Compound for forming organic film, and organic film composition using the same, process for forming organic film, and patterning process

ABSTRACT

The invention provides a compound for forming an organic film having a partial structure represented by the following formula (vii-2), 
     
       
         
         
             
             
         
       
     
     wherein R 1  represents a linear, branched or cyclic monovalent hydrocarbon group having 1 to 20 carbon atoms, and a methylene group constituting R 1  may be substituted by an oxygen atom; a+b is 1, 2 or 3; c and d are each independently 0, 1 or 2; x represents 0 or 1, when x=0, then a=c=0; L 7  represents a linear, branched or cyclic divalent organic group having 1 to 20 carbon atoms, L 8′  represents the partial structure represented by the following formula (i), 0≦o&lt;1, 0&lt;p≦1 and o+p=1, 
     
       
         
         
             
             
         
       
     
     wherein the ring structures Ar3 represent a substituted or unsubstituted benzene ring or naphthalene ring; R 0  represents a hydrogen atom or a linear, branched or cyclic monovalent organic group having 1 to 30 carbon atoms; and L 0  represents a divalent organic group. There can be provided an organic film composition for forming an organic film having high dry etching resistance as well as advanced filling/planarizing characteristics.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a resist underlayer film composition tobe used in a multilayer resist step which is used for a fine patterningin a manufacturing step of a semiconductor apparatus, etc., or anorganic film composition effective for a planarizing composition formanufacturing a semiconductor apparatus, a process for forming a filmusing the same, a patterning process using the underlayer compositionsuitable for exposure by far ultraviolet rays, KrF excimer laser (248nm), ArF excimer laser (193 nm), F₂ laser (157 nm), Kr₂ laser (146 nm),Ar₂ laser (126 nm), soft X-rays (EUV), electron beam (EB), an ion beam,X-rays, or the like, and a compound for forming an organic film usefulas a component of the film composition.

2. Description of the Related Art

With a tendency of high integration and high-speed of LSI, a finerpattern size is required. Along with the requirement of finer patternsize, the lithography technologies have accomplished fine patterning byusing light sources with shorter wavelength and properly selectingresist compositions corresponding to the light source. As for suchcompositions, positive photoresist compositions used as a monolayer aremainly selected. Each of these monolayer positive photoresistcompositions has a skeleton providing an etching resistance against dryetching with chlorine-based gas plasma or fluorine-based gas plasma inthe resist resin, and has resist mechanism that an exposed area turnssoluble, thereby forming a pattern by dissolving the exposed area anddry etching a substrate to be processed to which the resist compositionis applied by using the remained resist pattern as an etching mask.

However, when a pattern become finer, that is, a pattern width ischanged narrower, without changing the thickness of a photoresist filmto be used, resolution performance of the photoresist film is lowered.In addition, developing the pattern of the photoresist film with adeveloper causes a pattern fall because a so-called aspect ratio of thepattern becomes too high. Therefore, the thickness of a photoresist filmhas been made thinner along with advancing a finer pattern.

On the other hand, for processing a substrate to be processed, a methodto process the substrate by dry etching by using a pattern-formedphotoresist film as an etching mask is usually used. Actually however,there is no dry etching method capable of providing an absolute etchingselectivity between the photoresist film and the substrate to beprocessed. Therefore, the resist film is also damaged and fallen duringprocessing the substrate, so that the resist pattern cannot betransferred to the substrate to be processed correctly. Accordingly, asa pattern becomes finer, it has been required that a resist compositionhas a higher dry etching resistance. In addition, the use of shorterwavelength exposure radiations has required resins used for photoresistcompositions to have low absorbance at the wavelength to be used for theexposure. Accordingly, as the radiation shifts from i-beam to KrF and toArF, the resin shifts to novolac resins, polyhydroxystyrene, and resinshaving an aliphatic polycyclic skeleton. Along with this shift, anetching rate of the resin actually becomes higher under the dry etchingconditions mentioned above, and recent photoresist compositions having ahigh resolution tend to have a low etching resistance.

As a result, a substrate to be processed has to be dry etched with athinner photoresist film having lower etching resistance. The need toprovide a composition for this process and the process itself has becomeurgent.

A multilayer resist process is one of solutions for these problems. Thismethod is as follows: a middle layer film having a different etchingselectivity from a photoresist film, that is, a resist upper layer film,is set between the resist upper layer film and a substrate to beprocessed, and then, to obtain a pattern on the resist upper layer film;the resist upper layer pattern is transferred to the middle layer filmby dry etching by using the upper layer resist pattern as a dry etchingmask; and then the middle layer pattern is transferred to the substrateto be processed by dry etching by using the middle layer film as a dryetching mask.

The multi-layer resist process further include a three-layer resistprocess which can be performed by using a typical resist compositionused in a monolayer resist process. For example, this method isconfigured to form: an organic film based on novolac or the like as aresist underlayer film on a substrate to be processed; asilicon-containing film as a resist middle layer film thereon; and ausual organic photoresist film as a resist upper layer film thereon.Since the organic resist upper layer film exhibits an excellent etchingselectivity ratio relative to the silicon-containing resist middle layerfilm for dry etching by fluorine-based gas plasma, the resist pattern istransferred to the silicon-containing resist middle layer film by meansof dry etching based on fluorine-based gas plasma. Further, since thesilicon-containing resist middle layer film exhibits an excellentetching selectivity ratio relative to an organic underlayer in theetching using an oxygen gas or a hydrogen gas, film pattern of thesilicon-containing middle layer film is transferred to the underlayer bymeans of etching based on an oxygen gas or a hydrogen gas. According tothis process, even when a resist composition which is difficult to forma pattern having a sufficient film thickness for directly processing thesubstrate to be processed or a resist composition which has insufficientdry etching resistance for processing the substrate is used, a novolacresin film pattern having a sufficient dry etching resistance for theprocessing can be obtained when the pattern can be transferred to thesilicon-containing film.

While numerous process have been known (for example, Patent Document 1)for the organic underlayer film as described above, in recent years, ithas now been growing necessity to have excellent filling property andplanarizing characteristics in addition to dry etching characteristics.For example, when a basis substrate to be processed has a fine patternstructural composition such as a hole or a trench, it is necessary tohave filling property which fills in the pattern with a film without anyvoids. In addition, when the substrate to be processed as a basis has astep(s), or when a pattern dense portion and no pattern region exist onthe same substrate, it is necessary to planarizing the film surface bythe underlayer. By planarizing the surface of the underlayer,fluctuation in the film thickness of a middle layer or a photoresistformed thereon is controlled, whereby a focus margin in lithography or amargin in the processing step of the substrate to be processedthereafter can be enlarged.

As a means to improve filling/planarizing characteristics of anunderlayer composition, addition of a liquid state additive such as apolyether polyol has been proposed (Patent Document 2). However, theorganic film formed by the method contains a large amount of thepolyether polyol units, etching resistance of which are inferior, sothat the etching resistance of the resulting film is markedly loweredwhereby it is not suitable for an underlayer for the three-layer resist.Thus, it has been desired to develop a resist underlayer filmcomposition having both of excellent filling/planarizing characteristicsand sufficient etching resistance, and a patterning process using thesame.

Also, uses of an organic film composition excellent infilling/planarizing characteristics are not limited only to anunderlayer for the three-layer resist, and it can be widely applied as aplanarizing composition for manufacturing a semiconductor apparatus, forexample, substrate planarizing prior to patterning by nano imprinting,etc. Moreover, for global planarizing during the preparation process ofthe semiconductor apparatus, a CMP process has now generally been used,but the CMP is a high cost process, so that such a composition can beexpected to be a composition which is to bear the global planarizingmethod to be used in place of the CMP.

PRIOR ART DOCUMENTS Patent Documents [Patent Document 1] Japanese PatentLaid-Open Publication No. 2004-205685 [Patent Document 2] JapanesePatent No. 4784784 SUMMARY OF THE INVENTION

The present invention has been done in view of the situation asmentioned and an object thereof is to provide an organic filmcomposition for forming an organic film having high dry etchingresistance as well as advanced filling/planarizing characteristics.

In order to solve the problems, the present invention provides acompound for forming an organic film having a partial structurerepresented by the following formula (i) or (ii),

wherein the ring structures Ar1, Ar2 and Ar3 each represent asubstituted or unsubstituted benzene ring or naphthalene ring; e is 0 or1; R⁰ represents a hydrogen atom or a linear, branched or cyclicmonovalent organic group having 1 to 30 carbon atoms; L₀ represents alinear, branched or cyclic divalent organic group having 1 to 32 carbonatoms; and the methylene group constituting L₀ may be substituted by anoxygen atom or a carbonyl group.

Such a compound for forming an organic film enables to provide anorganic film composition for forming an organic film having high dryetching resistance as well as advanced filling/planarizingcharacteristics.

Also, the compound for forming an organic film containing a compoundrepresented by the following formula (iii) is provided,

wherein R¹ represents a linear, branched or cyclic monovalenthydrocarbon group having 1 to 20 carbon atoms, and the methylene groupconstituting R¹ may be substituted by an oxygen atom; a+b and a′+b′ areeach independently 1, 2 or 3; c, d, c′ and d′ are each independently 0,1 or 2; x and y each independently represent 0 or 1, when x=0, thena=c=0, and when y=0, then a′=c′=0; and L represents a partial structurerepresented by the formula (ii).

In this case, the compound represented by the formula (iii) ispreferably a compound containing an aliphatic hydrocarbon grouprepresented by the following formula (1),

wherein Ar1, Ar2, Ar3, R¹, a, b, a′, b′, c, d, c′, d′, x, y and e havethe same meanings as defined above; L₁ represents a linear, branched orcyclic divalent hydrocarbon group having 2 to 30 carbon atoms containingan aliphatic hydrocarbon group, and the methylene group constituting L₁may be substituted by an oxygen atom or a carbonyl group.

Further, the compound for forming an organic film having a partialstructure represented by the following formula (iv) is provided,

wherein R¹ represents a linear, branched or cyclic monovalenthydrocarbon group having 1 to 20 carbon atoms, and the methylene groupconstituting R¹ may be substituted by an oxygen atom; c, d, c′ and d′are each independently 0, 1 or 2; x and y each independently represent 0or 1, when x=0, then c=0, and when y=0, then c′=0; L represents apartial structure represented by the formula (ii); L₂ represents alinear, branched or cyclic divalent organic group having 2 to 30 carbonatoms; and the methylene group constituting L₂ may be substituted by anoxygen atom or a carbonyl group, and the hydrogen atom constituting thestructure may be substituted by a hydroxyl group.

In this case, the partial structure represented by the formula (iv) ispreferably a partial structure represented by the following formula (2),

wherein Ar1, Ar2, Ar3, R¹, c, d, c′, d′, x, y, e and L₂ have the samemeanings as defined above; L₁ represents a linear, branched or cyclicdivalent hydrocarbon group having 2 to 30 carbon atoms containing analiphatic hydrocarbon group, and the methylene group constituting L₁ maybe substituted by an oxygen atom or a carbonyl group.

Moreover, the compound for forming an organic film preferably contains apolymer compound having a partial structure represented by the followingformula (v),

wherein R¹, a, b, a′, b′, c, d, c′, d′, x, y and L have the samemeanings as defined above; L₃ represents a linear, branched or cyclicdivalent organic group having 1 to 20 carbon atoms, L₄ represents L₃,the partial structure represented by the formula (i), or the partialstructure represented by the formula (ii), and 0≦i≦1, 0≦j≦1 and i+j=1.

Furthermore, the compound for forming an organic film preferablycontains a polymer having a partial structure represented by thefollowing formula (vi),

wherein Ar1, Ar2, R¹, a, b, a′, b′, c, d, c′, d′, x and y have the samemeanings as defined above; L₅ represents a linear, branched or cyclicdivalent organic group having 1 to 20 carbon atoms, L₆ represents thepartial structure represented by the formula (i) or the partialstructure represented by the formula (ii), and 0≦m<1, 0<n≦1 and m+n=1.

Moreover, the compound for forming an organic film preferably contains apolymer having a partial structure represented by the following formula(vii),

wherein R¹, a, b, c, d and x have the same meanings as defined above; L₇represents a linear, branched or cyclic divalent organic group having 1to 20 carbon atoms, L₈ represents the partial structure represented bythe formula (i) or the partial structure represented by the formula(ii), and 0≦o<1, 0<p≦1 and o+p=1.

These compounds have a plural number of the aromatic rings, have highcarbon density, and show high dry etching resistance. Also, the L₁contains an aliphatic hydrocarbon structure so that the compoundcontains high flexibility which contributes to improvement infilling/planarizing characteristics. As a result, both of etchingcharacteristics and filling/planarizing characteristics can besatisfied.

By using such a compound for a resist underlayer film composition to beused for forming a multilayer resist film to be applied to a fineprocessing in the preparation step of a semiconductor apparatus, it ispossible to provide a resist underlayer film composition for forming aresist underlayer film having high dry etching resistance as well asadvanced filling/planarizing characteristics, a process for forming theresist underlayer film, and a patterning process. Also, it is alsopossible in the present invention to provide a planarizing compositionfor manufacturing a semiconductor apparatus having excellentfilling/planarizing characteristics, which can be applied forplanarizing in the preparation step of a semiconductor apparatus otherthan the multilayer resist process.

Also, it is provided an organic film composition using the compound forforming an organic film, which organic film composition comprises atleast one selected from

(A) the compound represented by the formula (iii), (B) the compoundhaving the partial structure represented by the formula (iv), (C-1) thepolymer compound having the partial structure represented by the formula(iv) as a part of the repeating unit, (C-2) the polymer compound havingthe partial structure represented by the formula (v), (C-3) the polymercompound having the partial structure represented by the formula (vi),and (C-4) the polymer compound having the partial structure representedby the formula (vii).

Such an organic film composition is suitable as an organic filmcomposition for manufacturing a semiconductor apparatus. That is, itprovides high dry etching resistance, and excellent filling/planarizingcharacteristics.

It is preferred that the organic film composition further contains (D) aresin containing an aromatic ring which is different from the (C-1) to(C-4).

By adding the (D) resin containing an aromatic ring to the organic filmcomposition, various characteristics required for an organic filmcomposition for manufacturing a semiconductor apparatus such as dryetching resistance, heat resistance and curability can be improved.Also, suitability of characteristics depending on the uses is possibleby optionally selecting a resin to be added.

It is preferred that the (D) resin containing an aromatic ring containsa naphthalene ring.

When (D) the resin containing an aromatic ring in the organic filmcomposition contains a naphthalene ring, it is possible to obtain anorganic film excellent in etching resistance, heat resistance andoptical characteristic.

Further, it is preferred that the (D) resin containing an aromatic ringcontains a resin (D-1) obtained by a polycondensation reaction of atleast one of compounds represented by the following formulae (3a) and(3b), with a compound represented by the following formula (4),

wherein each R² independently represent a hydrogen atom or a saturatedor unsaturated hydrocarbon group having 1 to 20 carbon atoms; each R³independently represent a benzene ring or a naphthalene ring; m1+m2,m3+m4 and m5+m6 are each 1 or 2; and n1, n2 and n3 are each 0 or 1,

A-CHO  (4)

wherein A represents either one of a hydrogen atom, a hydrocarbon grouphaving 1 to 10 carbon atoms and a substituted or unsubstituted aromatichydrocarbon group having 6 to 20 carbon atoms.

When the organic film composition contains (D) the resin containing anaromatic ring including Compound (D-1), it is preferred since the formedorganic film is excellent in filling/planarizing characteristics andparticularly excellent in etching resistance and heat resistance.

Also, it is preferred that the (D) resin containing an aromatic ringcontains (D-2) a resin having one or more repeating units represented bythe following formula (5),

wherein each R⁴ independently represent a hydrogen atom or a saturatedor unsaturated hydrocarbon group having 1 to 20 carbon atoms; R⁵represent a hydrogen atom or may form a ring by bonding to one of R⁴;when R⁴ and R⁵ are bonded to form a ring, —R⁴—R⁵— represents a singlebond or an alkylene group having 1 to 3 carbon atoms; m7+m8 represents0, 1 or 2; and n4 represents 0 or 1.

When the organic film composition contains (D) the resin containing anaromatic ring including Compound (D-2), it is preferred since the formedorganic film is excellent in filling/planarizing characteristics, andparticularly excellent in etching resistance and optical characteristic.

Also, the organic film composition may further contain at least one of(E) a compound containing a phenolic hydroxyl group, (F) an acidgenerator, (G) a cross-linking agent, (H) a surfactant, and (I) anorganic solvent.

Thus, into the organic film composition, (E) a compound containing aphenolic hydroxyl group, (F) an acid generator and (G) a cross-linkingagent can be added for further promoting a cross-linking reaction and(H) a surfactant can be also added for improving coatability in spincoating. Also, when (I) an organic solvent is added, the resultingorganic film composition composition is a solution, so that spin coatingcan be carried out.

Also, the organic film composition can be made to be used for a resistunderlayer film composition or a planarizing composition formanufacturing a semiconductor apparatus.

Thus, the organic film composition is used for forming a multilayerresist film to be applied to a fine processing in the preparationprocess of a semiconductor apparatus, it is possible to provide a resistunderlayer film composition for forming a resist underlayer film havingboth of high dry etching resistance and advanced filling/planarizingcharacteristics. In addition it is possible to provide a planarizingcomposition for manufacturing a semiconductor apparatus having excellentfilling/planarizing characteristics, which can be applied forplanarizing in the preparation process of a semiconductor apparatusother than the multilayer resist process.

Also, the present invention provides a process for forming an organicfilm which is a process for preparing an organic film to be used as aresist underlayer film or a planarizing film for manufacturing asemiconductor apparatus of a multilayer resist film used in lithography,which comprises coating the organic film composition on a substrate tobe processed, and subjecting the composition to heat treatment at atemperature of 100° C. or higher and 600° C. or lower for 10 seconds to600 seconds to form a cured film.

Thus, by coating the organic film composition and subjecting the organicfilm composition to heat treatment at a temperature of 100° C. or higherand 600° C. or lower for 10 seconds to 600 seconds whereby thecross-linking reaction can be promoted and mixing with the upper layerfilm can be prevented.

Also, the present invention provides a process for forming an organicfilm which is a process for preparing an organic film to be used as aresist underlayer film or a planarizing film for manufacturing asemiconductor apparatus of a multilayer resist film used in lithography,which comprises coating the organic film composition on a substrate tobe processed, and baking the composition in an atmosphere with an oxygenconcentration of 0.1% or more and 21% or less to form a cured film.

The organic film composition is baked in such an oxygen atmosphere,thereby enabling to obtain a fully cured film.

Also, as the substrate to be processed, a substrate having a structuralcomposition or step(s) each with a height of 30 nm or more can be used.

The organic film composition is excellent in filling/planarizingcharacteristics, so that it is particularly useful for forming aplanarizing organic film on the substrate having a structuralcomposition or step(s) each with a height of 30 nm or more.

Further, the present invention provides patterning process which is aprocess for forming a pattern on a substrate to be processed, whichcomprises the steps of, at least, forming a resist underlayer film onthe substrate to be processed by using the organic film composition;forming a resist middle layer film on the resist underlayer film byusing a resist middle layer film composition containing a silicon atom;forming a resist upper layer film on the resist middle layer film byusing a resist upper layer film composition comprising a photoresistcomposition, to form a multilayer resist film; conducting exposure of apattern circuit region of the resist upper layer film and thendeveloping it by a developer to form a resist pattern on the resistupper layer film; etching the resist middle layer film by using theobtained pattern-formed resist upper layer film as an etching mask;etching the resist underlayer film by using the obtained pattern-formedresist middle layer film as an etching mask; and etching the substrateto be processed by using the obtained pattern-formed resist underlayerfilm as an etching mask, to form a pattern on the substrate to beprocessed.

In such a multilayer resist process, it is the patterning process usingthe organic film composition, a fine pattern can be formed to thesubstrate to be processed with high precision.

In addition, etching of the resist underlayer film using the obtainedpattern-formed resist middle layer film as an etching mask can becarried out by using an etching gas mainly comprising an oxygen gas or ahydrogen gas.

The resist middle layer film containing a silicon atom shows etchingresistance to an oxygen gas or a hydrogen gas, so that etching of theresist underlayer film by using the resist middle layer film as a maskcan be carried out by using an etching gas mainly comprising an oxygengas or a hydrogen gas.

Further, the present invention provides a patterning process which is aprocess for forming a pattern on the substrate to be processed, andcomprises the steps of, at least, forming a resist underlayer film onthe substrate to be processed by using the organic film composition;forming an inorganic hard mask middle layer film selected from any oneof a silicon oxide film, a silicon nitride film and a silicon oxynitridefilm on the resist underlayer film; forming a resist upper layer film onthe inorganic hard mask middle layer film by using a resist upper layerfilm composition comprising a photoresist composition, to make amultilayer resist film; conducting exposure of a pattern circuit regionof the resist upper layer film and then developing it by a developer toform a resist pattern on the resist upper layer film; etching theinorganic hard mask middle layer film by using the obtained resistpattern as an etching mask; etching the resist underlayer film by usingthe obtained pattern-formed inorganic hard mask middle layer film as anetching mask; and etching the substrate to be processed by using theobtained pattern-formed resist underlayer film as an etching mask, toform a pattern on the substrate to be processed.

Moreover, the present invention is to provide a patterning process whichis a process for forming a pattern on the substrate to be processed,which comprises the steps of, at least, forming a resist underlayer filmon the substrate to be processed by using the organic film composition;forming an inorganic hard mask middle layer film selected from any oneof a silicon oxide film, a silicon nitride film and a silicon oxynitridefilm on the resist underlayer film; forming an organic antireflectionfilm on the inorganic hard mask middle layer film; forming a resistupper layer film on the organic antireflection film by using a resistupper layer film composition comprising a photoresist composition, tomake a multilayer resist film; conducting exposure of a pattern circuitregion of the resist upper layer film and then developing it by adeveloper to form a resist pattern on the resist upper layer film;etching the organic antireflection film and the inorganic hard maskmiddle layer film by using the obtained resist pattern as an etchingmask; etching the resist underlayer film by using the obtainedpattern-formed inorganic hard mask middle layer film as an etching mask;and etching the substrate to be processed by using the obtainedpattern-formed resist underlayer film as an etching mask, to form apattern on the substrate to be processed.

Thus, a resist middle layer film may be formed on a resist underlayerfilm, and an inorganic hard mask middle layer film selected from any oneof a silicon nitride film and a silicon oxynitride film may be formed onthe resist underlayer film. Further, a photoresist film may be formed onthe inorganic hard mask middle layer film as a resist upper layer film,and an organic antireflection film (BARC: bottom-anti-reflectivecoating) is formed on the inorganic hard mask middle layer film by spincoating, and a photoresist film may be formed thereon. When a siliconoxynitride film (SiON film) is used as a middle layer film, it isenabled to restrict reflection by virtue of the two-layer antireflectivefilms, i.e., the SiON film and BARC film, even by a liquid immersionexposure at a higher NA exceeding 1.0. Another merit of the formation ofthe BARC resides in obtainment of an effect to reduce footing of aphotoresist pattern compared to a photoresist pattern just above theSiON film.

Further, the inorganic hard mask middle layer film can be formed by theCVD method or the ALD method.

In the patterning process, the inorganic hard mask middle layer filmformed by the CVD method or the ALD method can be used in combinationwith the resist underlayer film formed by the spin coating method.

Also, as the substrate to be processed, a substrate having a structuralcomposition or a step(s) each with a height of 30 nm or more can beused.

The organic film composition is excellent in filling/planarizingcharacteristics, so that it is particularly useful for forming a patternon a substrate having a structural composition or step(s) each with aheight of 30 nm or more by a multilayer resist process lithography.

As explained above, the organic film composition using the compound forforming an organic film a polymer compound containing the compound as apart of the repeating unit has excellent filling/planarizingcharacteristics as well as does not impair other characteristics such asetching resistance, so that it is extremely useful as, for example, aresist underlayer film composition for a multilayer resist process or aplanarizing composition for manufacturing a semiconductor apparatus suchas a silicon-containing two-layer resist process, a three-layer resistprocess using a silicon-containing middle layer film, and a four-layerresist process using a silicon-containing middle layer film and anorganic antireflection film.

DESCRIPTION OF THE DRAWINGS

FIGS. 1A-1F are explanatory views of an example (three-layer resistprocess) of a patterning process using the present invention.

FIGS. 2G-2I are explanatory views of an evaluation method of fillingproperty.

FIGS. 3J-3K are explanatory views of an evaluation method of planarizingcharacteristics.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

For realizing characteristics required for a resist underlayer film, inparticular, characteristics such as etching resistance, heat resistance,and causing no occurrence of wiggling during etching of a substrate, afilm having a high carbon atom density and a low hydrogen atom densityis required. The present inventors have researched variously about acomposition for an underlayer having a high carbon atom density and alow hydrogen atom density, and they have developed a biphenyl derivativerepresented by the following formula (6):

wherein the ring structures Ar1 and Ar2 each represents a benzene ringor a naphthalene ring; each and x and y independently represent 0 or 1.

The biphenyl derivative has two fluorene structures and aphenol/naphthol structure in the molecule, has high carbon atom density(has low hydrogen atom density), and has excellent dry etchingresistance. In addition, phenol/naphthol structures having a heat/acidcross-linking reactivity are effectively provided at the both ends ofthe molecule so that sufficient curability can be shown at the time offilm formation.

Moreover, the present inventors thought to develop formulationcomponents specialized in improvement of the characteristics bymodifying the structure of the biphenyl derivative, to comply with therequirement to improve filling/planarizing characteristics that had beenin demand in recent years. As a result, they have found out thatadvanced filling/planarizing characteristics have been realized by usinga compound into which a structure having flexibility, that is, a partialstructure represented by the following formula (i) or (ii) as a divalentorganic group containing an aliphatic hydrocarbon group or a polyethergroup is introduced in place of a rigid biphenyl structure. And, thecompound represented by the following formula (iii) which is a compoundinto which a partial structure represented by the following formula (i)or (ii) is introduced showed high dry etching resistance and sufficientcuring reactivity at the time of an organic film as expected. Also, inthe compound having a partial structure represented by the followingformula (iv) which is based on the similar design as above, it has beenfound that high dry etching resistance and excellent filling/planarizingcharacteristics can be simultaneously realized, whereby they haveaccomplished the present invention.

In the following, the present invention is explained in more detail.

The most important structure possessed by the compound provided by thepresent invention is a partial structure represented by the followingformula (i) or (ii),

wherein the ring structures Ar1, Ar2 and Ar3 each represent asubstituted or unsubstituted benzene ring or naphthalene ring; e is 0 or1; R⁰ represents a hydrogen atom or a linear, branched or cyclicmonovalent organic group having 1 to 30 carbon atoms; L₀ represents alinear, branched or cyclic divalent organic group having 1 to 32 carbonatoms; and the methylene group constituting L₀ may be substituted by anoxygen atom or a carbonyl group.

The compound for forming an organic film into which the structures areintroduced has fluorene structures and a phenol/naphthol structure inthe molecule, has high carbon atom density (has low hydrogen atomdensity), and has excellent dry etching resistance. In addition,phenol/naphthol structures having a heat/acid cross-linking reactivityare effectively provided at the both ends of the molecule so thatsufficient curability can be shown at the time of film formation.Moreover, by incorporating an aliphatic hydrocarbon group havingflexibility or a divalent organic group containing a polyether group, anorganic film composition which shows advanced filling/planarizingcharacteristics, and has high dry etching resistance and excellentfilling/planarizing characteristics can be obtained.

Ar3 in the formula (i) or (ii) represents a benzene ring or anaphthalene ring. Specifically the partial structures shown below may bepreferably exemplified.

Ar3 may be substituted by a linear, branched or cyclic monovalenthydrocarbon group having 1 to 20 carbon atoms, and the methylene groupconstituting the monovalent hydrocarbon group may be substituted by anoxygen atom. The monovalent hydrocarbon group may be specificallyexemplified by a methyl group, an ethyl group, an n-propyl group, anisopropyl group, an n-butyl group, a sec-butyl group, a tert-butylgroup, an n-pentyl group, a neopentyl group, an n-hexyl group, ann-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, ann-dodecyl group, an n-pentadecyl group, an n-eicosyl group, acyclopentyl group, a cyclohexyl group, a cyclopentylmethyl group, acyclohexylmethyl group, a cyclopentylethyl group, a cyclohexylethylgroup, a cyclopentylbutyl group, a cyclohexylbutyl group and anadamantyl group.

By introducing Ar3, dry etching resistance can be improved. Also, ascompared with the case where, as L₀ of the compound represented by theformula (i) or (ii), for example, a polymethylene group, etc., isintroduced and made e=0, there is a superior point in synthesis that aby-product(s) difficultly formed.

Ar1 and Ar2 in the formula (ii) each represents a benzene ring or anaphthalene ring.

A fluorine ring structure and a benzofluorene structure are particularlypreferred as the partial structure. In addition, the hydrogen atom inthese groups may be substituted by a halogen atom, a hydrocarbon group,a hydroxyl group, an alkoxy group, a nitro group or a cyano group.Specific partial structures are exemplified below.

R₀ in the formula (i) or (ii) represents a linear, branched or cyclicmonovalent hydrocarbon group having 1 to 20 carbon atoms, and themethylene group constituting the may hydrocarbon group be substituted byan oxygen atom. The monovalent hydrocarbon group may be specificallyexemplified by a methyl group, an ethyl group, an n-propyl group, anisopropyl group, an n-butyl group, a sec-butyl group, a tert-butylgroup, an n-pentyl group, a neopentyl group, an n-hexyl group, ann-heptyl group, an n-octyl group, an n-nonyl group, an n-decyl group, ann-dodecyl group, an n-pentadecyl group, an n-eicosyl group, acyclopentyl group, a cyclohexyl group, a cyclopentylmethyl group, acyclohexylmethyl group, a cyclopentylethyl group, a cyclohexylethylgroup, a cyclopentylbutyl group, a cyclohexylbutyl group, an adamantylgroup, a methoxy group, an ethoxy group, a propoxy group, a butoxygroup, a pentoxy group, a hexyloxy group, a heptoxy group, amethoxyethoxy group and an ethoxyethoxy group.

L₀ in the formula (i) or (ii) represents a linear, branched or cyclicdivalent organic group having 1 to 32 carbon atoms; and the methylenegroup constituting it may be substituted by an oxygen atom or a carbonylgroup. Such a divalent organic group may be specifically exemplified bythe following.

Next, as a process for preparing the partial structure represented bythe formula (i), the methods shown by the following reaction schemes areexemplified,

wherein D represents a protective group for an alcohol against anorganometal; E represents an eliminatable group on the aromatic ring toan organometallic reagent; M represents Li or MgX, where X represents ahalogen atom; and L₀, R⁰ and Ar3 have the same meanings as definedabove.

wherein E′ represents an eliminatable group which eliminates with thehydroxyl group by an etherification reaction; L₁ represents a linear,branched or cyclic divalent hydrocarbon group having 2 to 30 carbonatoms containing an aliphatic hydrocarbon group; and R⁰ and Ar3 have thesame meanings as defined above.

wherein E′, L₁, R⁰ and Ar3 have the same meanings as defined above.

wherein E″ represents an eliminatable group to the aromaticelectrophilic reagent in the Friedel-Crafts reaction; and L₀, R⁰ and Ar3have the same meanings as defined above.

Next, as a process for preparing the partial structure represented bythe formula (ii), the methods shown by the following reaction schemes 1Band 2B are exemplified,

wherein Ar1, Ar2, Ar3, L₀ and M have the same meanings as defined above.

As the organometallic reagent to be used in the reaction scheme 1A,Grignard reagents, organolithium reagents, organozinc reagents andorganotitanium reagents are exemplified, and Grignard reagents andorganolithium reagents are particularly preferred. The Grignard reagentand the organolithium reagent may be prepared by direct metallation of acorresponding halide and metal magnesium or metal lithium, or may beformed by a metal-halogen exchange reaction with an isopropyl magnesiumhalide or an aliphatic organometallic compound such as methyl lithiumand butyl lithium. Also, the organozinc reagent or the organotitaniumreagent can be prepared from a corresponding Grignard reagent ororganolithium reagent by the reaction with a zinc halide, a titanium(IV)halide or a titanium(IV) alkoxide. At the time of preparing theorganometallic reagent (1A-IIa), or at the time of reacting theorganometallic reagent and the aromatic compound (1A-Ia), a metal saltcompound may be co-presented. At this time, the reaction proceedssmoothly by the presence of a transition metal catalyst such aspalladium and nickel. The metal salt compound may be mentioned acyanide, a halide and a perhalogenic acid salt, and particularly alithium salt such as lithium chloride, lithium bromide, lithium iodideand lithium perchlorate, and a copper salt such as copper(I) cyanide,copper(II) cyanide, copper(I) chloride, copper(II) chloride anddilithium tetrachlorocuprate are preferably exemplified. The metal saltcompound is added in an amount of 0.01 to 5.0 equivalents, preferably0.2 to 2.0 equivalents based on an amount of the organometallic reagent,whereby the solubility of the organometallic reagent is increased tomake it easily prepared, and, nucleophilicity or Lewis acidity of thereagent can be controlled. The solvent to be used for preparing theorganometallic reagent (1A-IIa) and in the reaction with the aromaticcompound (1A-Ia) may be mentioned an ether such as diethyl ether,dibutyl ether, tetrahydrofuran, 1,4-dioxane and cyclopentyl methylether; a hydrocarbon such as benzene, toluene, xylene, mesitylene,hexane, heptane, octane and isooctane; an aprotic polar solvent such asN,N,N′,N′-tetramethylethylenediamine, hexamethylphosphoric triamide andN,N-dimethylformamide, singly or in admixture. The reaction temperaturemay vary depending on a kind of the aromatic compound (1A-Ia) or theorganometallic reagent (1A-IIa) and reaction conditions, and preferably−70 to 150° C. For example, in the case of an organozinc reagent or aGrignard reagent as (1A-IIa), it can be variously selected from roomtemperature to under reflux at the boiling point of the solvent. Thereaction time is desirably determined by tracing the reaction usingchromatography to complete the reaction, and it is generally carried outfrom 30 minutes to 48 hours.

As the protective group for an alcohol to be used in the reaction scheme1A, those generally known may be used, and an acetal group or a silylgroup is preferred.

As the organometallic reagent to be used in the reaction schemes 1B and2B, Grignard reagents, organolithium reagents, organozinc reagents andorganotitanium reagents are exemplified, and Grignard reagents andorganolithium reagents are particularly preferred. The Grignard reagentand the organolithium reagent may be prepared by direct metallation of acorresponding halide and metal magnesium or metal lithium, or may beformed by a metal-halogen exchange reaction with an isopropyl magnesiumhalide or an aliphatic organometallic compound such as methyl lithiumand butyl lithium. Also, the organozinc reagent or the organotitaniumreagent can be prepared from a corresponding Grignard reagent ororganolithium reagent by the reaction with a zinc halide, a titanium(IV)halide or a titanium(IV) alkoxide. At the time of preparing theorganometallic reagent (1B-IIb) or (2B-IIb′), or at the time of reactingthe organometallic reagent and the ketone compound (1B-Ib, 2B-Ib′), ametal salt compound may be co-presented. The metal salt compound may bementioned a cyanide, a halide and a perhalogenic acid salt, andparticularly a lithium salt such as lithium chloride, lithium bromide,lithium iodide and lithium perchlorate, and a copper salt such ascopper(I) cyanide, copper(II) cyanide, copper(I) chloride, copper(II)chloride and dilithium tetrachlorocuprate are preferably exemplified.The metal salt compound is added in an amount of 0.01 to 5.0equivalents, preferably 0.2 to 2.0 equivalents based on an amount of theorganometallic reagent, whereby the solubility of the organometallicreagent is increased to make it easily prepared, and, nucleophilicity orLewis acidity of the reagent can be controlled. The solvent to be usedfor preparing the organometallic reagent (1B-IIb) or (2B-IIb′) and inthe reaction with the ketone compound (1B-Ib, 2B-Ib′) may be mentionedan ether such as diethyl ether, dibutyl ether, tetrahydrofuran,1,4-dioxane and cyclopentyl methyl ether; a hydrocarbon such as benzene,toluene, xylene, mesitylene, hexane, heptane, octane and isooctane; anaprotic polar solvent such as N,N,N′,N′-tetramethylethylenediamine,hexamethylphosphoric triamide and N,N-dimethylformamide, singly or inadmixture. The reaction temperature may vary depending on a kind of theketone compound (1B-Ib, 2B-Ib′) or the organometallic reagent (1B-IIb)or (2B-IIb′) and reaction conditions, and, for example, in the case ofan organolithium reagent as (1B-IIb) or (2B-IIb′), it is −70 to 0° C.and in the case of a Grignard reagent, it can be variously selected fromroom temperature to under reflux at the boiling point of the solvent.The reaction time is desirably determined by tracing the reaction usingchromatography to complete the reaction, and it is generally carried outfrom 30 minutes to 48 hours.

As an example of the reaction of the reaction scheme 2A,

P1) condensation reaction with an organic halogen compound andP2) condensation reaction with a polyolare mentioned below specifically.P1) Condensation Reaction with an Organic Halogen Compound

The condensation reaction of the aromatic compound (2A-Ia′) and theorganic halogen compound is generally carried out in the absence of asolvent or in a solvent at room temperature, or under cooling or underheating, if necessary.

The organic halogen compound may be specifically exemplified by adihaloalkane such as 1,2-dichloroethane, 1,2-dibromoethane,1,3-dichloropropane, 1,3-dibromopropane, 1,3-diiodopropane,1,4-dichlorobutane, 1,4-dibromobutane, 1-bromo-4-chlorobutane,1,4-diiodobutane, 1,5-dichloropentane, 1,5-dibromopentane,1,5-diiodopentane, 1,6-dichlorohexane, 1,6-dibromohexane,1-bromo-6-chloro-hexane, 1,6-diiodohexane, 1,7-dibromoheptane,1,8-dibromooctane, 1,9-dibromononane, 1,10-dibromodecane,1,12-dibromododecane, α,α′-dibromo-m-xylene, α,α′-dibromo-o-xylene,α,α′-dibromo-p-xylene, 2,5-bromomethylnaphthalene,2,6-bromomethylnaphthalene, 2,7-bromomethylnaphthalene and1,8-bromomethylnaphthalene; an epihalohydrin such as epifluorohydrin,epichlorohydrin, epibromohydrin, epiiodohydrin andβ-methylepichlorohydrin, but the invention is not limited by these.These organic halogen compounds may be used alone or may be used incombination of two or more kinds.

An amount of the organic halogen compound is preferably 0.05 to 5 mol,more preferably 0.1 to 1.5 mol based on 1 mol of the compoundrepresented by the formula (I).

The condensation reaction with the organic halogen compound ispreferably carried out under basic conditions. The base to be used maybe exemplified by an inorganic base such as sodium hydroxide, potassiumhydroxide, barium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, lithium hydride, sodium hydride,potassium hydride and calcium hydride; an alkyl metal such as methyllithium, n-butyl lithium, methylmagnesium chloride and ethylmagnesiumbromide; an alkoxide such as sodium methoxide, sodium ethoxide andpotassium t-butoxide; and an organic base such as triethylamine,diisopropylethylamine, N,N-dimethylaniline, pyridine and4-dimethylaminopyridine. An amount of the base to be used is preferably1.0 to 5.0 mol, more preferably 2.0 to 3.0 mol based on 1 mol of thecompound represented by the formula (I). As the method of the reaction,there is a method in which the compound represented by the formula (I),the organic halogen compound and a base are charged at once, or a methodin which an optional component is added dropwise. The base or metalimpurities can be removed by the usual aqueous post-treatment. Asothers, by adding a poor solvent and separating the poor solvent layer,starting composition(s) or low molecular weight polymer fraction(s) canbe removed. Moreover, if necessary, an amount of the metal impuritiescan be reduced by passing through a metal-removing filter. Thesepurification treatments may be carried out singly or may be carried outin combination of two or more kinds.

The solvent to be used in the condensation reaction may be exemplifiedby an ether such as diethyl ether, dibutyl ether, diethylene glycoldiethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and1,4-dioxane; a chlorine solvent such as methylene chloride, chloroform,dichloroethane and trichloroethylene; a hydrocarbon such as hexane,heptane, benzene, toluene, xylene and cumene; a nitrile such asacetonitrile; a ketone such as acetone, ethyl methyl ketone and isobutylmethyl ketone; an ester such as ethyl acetate, n-butyl acetate andpropylene glycol methyl ether acetate; and an aprotic polar solvent suchas dimethylsulfoxide, N,N-dimethylformamide, hexamethylphosphorictriamide and N-methyl-2-pyrrolidone, and these may be used alone or maybe used in combination of two or more kinds. The reaction may be carriedout by two-layer using the organic solvent and water, and in this case,to proceed the reaction rapidly, there may be added a phase-transfercatalyst such as tetramethylammonium chloride, tetraethylammoniumbromide, tetraethylammonium chloride, tetrapropylammonium bromide,tetrapropylammonium hydroxide, tetrabutylammonium bromide,tetrabutylammonium hydroxide, tetrabutylammonium hydrogen sulfate,tributylmethylammonium chloride, trioctylmethylammonium chloride,trilaurylmethylammonium chloride, benzyltrimethylammonium chloride,benzyltrimethylammonium hydroxide, benzyltriethylammonium chloride,benzyltributylammonium chloride and phenyltrimethylammonium chloride.

A reaction temperature of the condensation reaction is preferably from−50° C. to the boiling point of the solvent, more preferably roomtemperature to 150° C.

P2) Condensation Reaction with a Polyol

The condensation reaction of the aromatic compound (2A-Ia′) and a polyolis generally carried out in the absence of a solvent or in a solvent, atroom temperature or under cooling or under heating, if necessary.

The polyol may be exemplified by ethylene glycol, polyethylene glycolsuch as diethylene glycol, triethylene glycol, tetraethylene glycol,pentaethylene glycol and hexaethylene glycol; propylene glycol, andglycerin, but the invention is not limited by these. These polyols maybe used alone or may be used in combination of two or more kinds.

An amount of the polyol to be used is preferably 0.1 to 10.0 mol, morepreferably 0.3 to 5.0 mol based on 1 mol of the compound represented bythe formula (I).

In the condensation reaction, a catalyst may be used. An acid catalystis particularly preferred. The acid catalyst which can be used may bementioned an inorganic acid such as hydrochloric acid, hydrobromic acid,nitric acid, sulfuric acid, formic acid, phosphoric acid and heteropolyacid; an organic acid such as oxalic acid, acetic acid, trifluoroaceticacid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acidand trifluoromethanesulfonic acid; and a Lewis acid such as aluminumtrichloride, aluminum ethoxide, aluminum isopropoxide, borontrifluoride, boron trichloride, boron tribromide, tin tetrachloride, tintetrabromide, dibutyltin dichloride, dibutyltin dimethoxide, dibutyltinoxide, titanium tetrachloride, titanium tetrabromide, titanium(IV)methoxide, titanium(IV) ethoxide, titanium(IV) isopropoxide andtitanium(IV) oxide. More specifically, there may be mentioned an acidcatalyst such as hydrochloric acid, nitric acid, sulfuric acid, formicacid, oxalic acid, acetic acid, methanesulfonic acid, camphorsulfonicacid, p-toluenesulfonic acid and trifluoromethanesulfonic acid. Anamount of these acid catalysts is preferably 0.1 to 50.0 mol based on 1mol of the compound represented by the formula (I). As the method of thereaction, there is a method in which the compound represented by theformula (I), a polyol and a catalyst are charged at once, or a method inwhich an optional component is added dropwise. After completion of thereaction, to remove unreacted starting composition(s) or a catalystexisting in the reaction system, a temperature of the reaction vessel israised to 130 to 230° C., and a volatile component(s) can be removed at1 to 50 mmHg. The catalyst or metal impurities can be removed by theusual aqueous post-treatment. As others, by adding a poor solvent andseparating the poor solvent layer, starting composition(s) or lowmolecular weight polymer fraction(s) can be removed. Moreover, ifnecessary, an amount of the metal impurities can be reduced by passingthrough a metal-removing filter. These purification treatments may becarried out singly or may be carried out in combination of two or morekinds.

The solvent to be used in the condensation reaction may be exemplifiedby an alcohol such as methanol, ethanol, isopropyl alcohol, butanol,ethylene glycol, propylene glycol, diethylene glycol and glycerol; anether such as ethylene glycol monomethyl ether, propylene glycolmonomethyl ether, diethyl ether, dibutyl ether, diethylene glycoldiethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and1,4-dioxane; a chlorine solvent such as methylene chloride, chloroform,dichloroethane and trichloroethylene; a hydrocarbon such as hexane,heptane, benzene, toluene, xylene and cumene; a nitrile such asacetonitrile; a ketone such as acetone, ethyl methyl ketone and isobutylmethyl ketone; an ester such as ethyl acetate, n-butyl acetate andpropylene glycol methyl ether acetate; and an aprotic polar solvent suchas dimethylsulfoxide, N,N-dimethylformamide and hexamethylphosphorictriamide, and these may be used alone or may be used in combination oftwo or more kinds.

A reaction temperature of the condensation reaction is preferably from−50° C. to the boiling point of the solvent, more preferably roomtemperature to 150° C.

In the reaction scheme 3A, the objective composition can be obtained byreducing the formyl group contained in the ether compound prepared bythe reaction scheme 2A.

As the reducing agent, a generally known compound such as sodiumboronhydride and lithium aluminum hydride can be used. A reactiontemperature is possible between −70° C. and 150° C., and it isoptionally selectable in view of a reaction rate or the like.

The solvent to be used may be mentioned an ether such as diethyl ether,dibutyl ether, tetrahydrofuran, 1,4-dioxane and cyclopentyl methylether; a hydrocarbon such as benzene, toluene, xylene, mesitylene,hexane, heptane, octane and isooctane; an aprotic polar solvent such asN,N,N′,N′-tetramethylethylenediamine, hexamethylphosphoric triamide andN,N-dimethylformamide, singly or in admixture.

As an example of the reaction according to the reaction scheme 4A, theremay be exemplified acylation according to an aromatic electrophilicsubstitution reaction of a Lewis acid and an acid halide. Thissubstitution reaction is generally carried out in the absence of asolvent or in a solvent at room temperature, or under cooling or underheating, if necessary.

As the Lewis acid, those generally known such as boron trifluoride,aluminum trichloride and iron trichloride can be used. As the acidhalide to be used, there may be exemplified by succinyl chloride andadipoyl chloride. The solvent may be exemplified by a halogenatedhydrocarbon such as carbon disulfide, dichloromethane, chloroform,carbon tetrachloride and dichloroethylene; and nitrobenzene.

These compounds can be used not only as a preparation intermediate ofthe compound for forming an organic film, but also, by further acting onthe obtained compound for forming an organic film, to form a polymer,whereby an organic film composition can be formed.

In the present invention, a compound represented by the followingformula (iii) utilizing a partial structure represented by the formula(ii) obtained as mentioned above can be used.

wherein the ring structures Ar1, Ar2 and Ar3 each represent asubstituted or unsubstituted benzene ring or naphthalene ring; R¹represents a linear, branched or cyclic monovalent hydrocarbon grouphaving 1 to 20 carbon atoms, the methylene group constituting R¹ may besubstituted by an oxygen atom; a+b and a′+b′ are each independently 1, 2or 3; c, d, c′ and d′ are each independently 0, 1 or 2; x and y eachindependently represent 0 or 1, when x=0, then a=c=0, and when y=0, thena′=c′=0; e is 0 or 1; and L represents a partial structure representedby the formula (ii).

The compound for forming an organic film represented by the formula(iii) has fluorene structures and a phenol/naphthol structure in themolecule, has high carbon atom density (has low hydrogen atom density),and has excellent dry etching resistance. In addition, phenol/naphtholstructures having a heat/acid cross-linking reactivity are effectivelyprovided at the both ends of the molecule so that sufficient curabilitycan be shown at the time of film formation. Moreover, by introducing analiphatic hydrocarbon group having flexibility and a divalent organicgroup containing a polyether group in place of a rigid biphenylstructure, an organic film composition showing advancedfilling/planarizing characteristics and having high dry etchingresistance and excellent filling/planarizing characteristics isprovided.

Each x and y in the partial structure of the formula (iii) independentlyrepresent 0 or 1. Also, a+b and a′+b′ are each independently 1, 2 or 3.c, d, c′ and d′ are each independently 0, 1 or 2. When x=0, then, a=c=0,and when y=0, then, a′=c′=0.

The partial structure may be preferably exemplified by the followingstructures (the dotted line represents a bonding arm.).

R¹ in the formula (iii) represents a linear, branched or cyclicmonovalent hydrocarbon group having 1 to 20 carbon atoms, and themethylene group constituting the same may be substituted by an oxygenatom. The monovalent hydrocarbon group may be specifically exemplifiedby a methyl group, an ethyl group, an n-propyl group, an isopropylgroup, an n-butyl group, a sec-butyl group, a tert-butyl group, ann-pentyl group, a neopentyl group, an n-hexyl group, an n-heptyl group,an n-octyl group, an n-nonyl group, an n-decyl group, an n-dodecylgroup, an n-pentadecyl group, an n-eicosyl group, a cyclopentyl group, acyclohexyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, acyclopentylethyl group, a cyclohexylethyl group, a cyclopentylbutylgroup, a cyclohexylbutyl group and an adamantyl group.

As a preferred form of the compound represented by the formula (iii), acompound containing an aliphatic hydrocarbon group represented by thefollowing formula (1) may be mentioned.

wherein the ring structures Ar1, Ar2 and Ar3 each represent asubstituted or unsubstituted benzene ring or naphthalene ring; R¹represents a linear, branched or cyclic monovalent hydrocarbon grouphaving 1 to 20 carbon atoms, the methylene group constituting R¹ may besubstituted by an oxygen atom; a+b and a′+b′ are each independently 1, 2or 3; c, d, c′ and d′ are each independently 0, 1 or 2; x and y eachindependently represent 0 or 1, when x=0, then a=c=0, and when y=0, thena′=c′=0; e is 0 or 1; L₁ represents a linear, branched or cyclicdivalent hydrocarbon group having 2 to 30 carbon atoms containing analiphatic hydrocarbon group, and the methylene group constituting L₁ maybe substituted by an oxygen atom or a carbonyl group.

The compound containing an aliphatic hydrocarbon group represented bythe formula (1) has two fluorene structures and a phenol/naphtholstructure in the molecule, has high carbon atom density (has lowhydrogen atom density), and has excellent dry etching resistance. Inaddition, phenol/naphthol structures having a heat/acid cross-linkingreactivity are effectively provided at the both ends of the molecule sothat sufficient curability can be shown at the time of film formation.Moreover, by introducing a divalent hydrocarbon group containing analiphatic hydrocarbon group having flexibility in place of a rigidbiphenyl structure, an organic film composition showing advancedfilling/planarizing characteristics, and having high dry etchingresistance and excellent filling/planarizing characteristics isprovided.

L₁ in the formula (1) represents a linear, branched or cyclic divalenthydrocarbon group having 2 to 30 carbon atoms containing an aliphatichydrocarbon group, and the methylene group constituting the same may besubstituted by an oxygen atom or a carbonyl group. The divalenthydrocarbon group may be specifically exemplified by a group in whichtwo hydrogen atoms are removed from ethane, propane, propylene,n-butane, 1-butene, 2-butene, isobutane, n-pentane, n-hexane, n-heptane,n-octane, n-nonane, n-decane, n-dodecane, n-eicosane, n-triacontane,1,4-dimethylcyclohexane, 1,3-dimethyladamantane, o-xylene, m-xylene,p-xylene, 2,5-dibutyl-p-xylene, 2,5-dibutoxy-p-xylene,2,5-dioctyl-p-xylene, 2,5-dioctyloxy-p-xylene, 1,4-dimethylnaphthalene,1,5-dimethylnaphthalene, 2,6-dimethylnaphthalene and2,7-dimethylnaphthalene.

More preferred form of the compound represented by the formula (iii) maybe mentioned a compound represented by the following formula (7),

wherein the ring structures Ar1, Ar2 and Ar3 each represent asubstituted or unsubstituted benzene ring or naphthalene ring; R¹represents a linear, branched or cyclic monovalent hydrocarbon grouphaving 1 to 20 carbon atoms, R¹ and the methylene group constituting thesame may be substituted by an oxygen atom; a+b and a′+b′ are eachindependently 1, 2 or 3; c, d, c′ and d′ are each independently 0, 1 or2; x and y each independently represent 0 or 1, when x=0, then a=c=0,and when y=0, then a′=c′=0; L₁ represents a linear, branched or cyclicdivalent hydrocarbon group having 2 to 30 carbon atoms containing analiphatic hydrocarbon group, and the methylene group constituting L₁ maybe substituted by an oxygen atom or a carbonyl group.

As a typical example in the preparation process of the compoundrepresented by the formula (7) (e=1) or (8) (e=0) which is an example ofthe formula (1), there is a route in which an intermediate product (11)(above-mentioned IIIb′) or (13) (above-mentioned IIIb) is obtained bythe addition reaction of an organometallic reagent (10) (above-mentionedIIb′) or (12) (above-mentioned IIb) to the following ketone compound (9)(above-mentioned Ib and Ib′), and a phenol or naphthol analogues is/arereacted thereto to obtain (7) or (8), but the preparation method of thecompound is not limited by the method. In the case of the followingmethod, the organometallic reagent (10) or (12) is preferably used in anamount of 0.1 to 20 mol, particularly 0.25 to 0.5 mol based on 1 mol ofthe ketone compound of the formula (9),

wherein the ring structures Ar1, Ar2 and Ar3 each represent asubstituted or unsubstituted benzene ring or naphthalene ring; R¹represents a linear, branched or cyclic monovalent hydrocarbon grouphaving 1 to 20 carbon atoms, and the methylene group constituting R¹ maybe substituted by an oxygen atom; a+b and a′+b′ are each independently1, 2 or 3; c, d, c′ and d′ are each independently 0, 1 or 2; x and yeach independently represent 0 or 1, when x=0, then a=c=0, and when y=0,then a′=c′=0; L₁ represents a linear, branched or cyclic divalenthydrocarbon group having 2 to 30 carbon atoms containing an aliphatichydrocarbon group, and the methylene group constituting L₁ may besubstituted by an oxygen atom or a carbonyl group; and M represents Lior MgX, where X represents a halogen atom.

The organometallic reagent (10) or (12) may be exemplified by a Grignardreagent, an organolithium reagent, an organozinc reagent and anorganotitanium reagent, and a Grignard reagent and an organolithiumreagent are particularly preferred. The Grignard reagent and theorganolithium reagent can be prepared by direct metallation of acorresponding halide and metal magnesium or metal lithium, or by ametal-halogen exchange reaction with an isopropyl magnesium halide or analiphatic organometallic compound such as methyl lithium and butyllithium. Also, the organozinc reagent or the organotitanium reagent canbe prepared from a corresponding Grignard reagent or organolithiumreagent by the reaction with a zinc halide, a titanium(IV) halide or atitanium(IV) alkoxide. At the time of preparing the organometallicreagent (10) or (12), or at the time of reacting the organometallicreagent and the ketone compound (9), a metal salt compound may beco-presented. The metal salt compound may be mentioned a cyanide, ahalide and a perhalogenic acid salt, and particularly a lithium saltsuch as lithium chloride, lithium bromide, lithium iodide and lithiumperchlorate, and a copper salt such as copper(I) cyanide, copper(II)cyanide, copper(I) chloride, copper(II) chloride and dilithiumtetrachlorocuprate are preferably exemplified. The metal salt compoundis added in an amount of 0.01 to 5.0 equivalents, preferably 0.2 to 2.0equivalents based on an amount of the organometallic reagent, wherebythe solubility of the organometallic reagent is increased to make iteasily prepared, or, nucleophilicity or Lewis acidity of the reagent canbe controlled. The solvent to be used for preparing the organometallicreagent (10) or (12) and in the reaction with the ketone compound (9)may be mentioned an ether such as diethyl ether, dibutyl ether,tetrahydrofuran, 1,4-dioxane and cyclopentyl methyl ether; a hydrocarbonsuch as benzene, toluene, xylene, mesitylene, hexane, heptane, octaneand isooctane; an aprotic polar solvent such asN,N,N′,N′-tetramethylethylenediamine, hexamethylphosphoric triamide andN,N-dimethylformamide, singly or in admixture. The reaction temperaturemay vary depending on a kind of the ketone compound (9) or theorganometallic reagent (10) or (12) and reaction conditions, andpreferably −70 to 150° C. For example, in the case of an organozincreagent as (10) or (12), it is −70 to 0° C., and in the case of aGrignard reagent, it can be variously selected from room temperature tounder reflux at the boiling point of the solvent.

The dehydration condensation reaction of the intermediate product (11)or (13) and a phenol or naphthol analogue is generally carried out byusing an acid as a catalyst in the absence of a solvent or in a solventat room temperature, or under cooling or under heating, if necessary.The solvent to be used may be exemplified by an alcohol such asmethanol, ethanol, isopropyl alcohol, butanol, ethylene glycol,propylene glycol, diethylene glycol and glycerol; an ether such asethylene glycol monomethyl ether, propylene glycol monomethyl ether,diethyl ether, dibutyl ether, diethylene glycol diethyl ether,diethylene glycol dimethyl ether, tetrahydrofuran and 1,4-dioxane; achlorine solvent such as methylene chloride, chloroform, dichloroethaneand trichloroethylene; a hydrocarbon such as hexane, heptane, benzene,toluene, xylene and cumene; a nitrile such as acetonitrile; a ketonesuch as acetone, ethyl methyl ketone and isobutyl methyl ketone; anester such as ethyl acetate, n-butyl acetate and propylene glycol methylether acetate; and an aprotic polar solvent such as dimethylsulfoxide,N,N-dimethylformamide and hexamethylphosphoric triamide, and these maybe used alone or may be used in combination of two or more kinds. Theacid catalyst to be used may be mentioned an inorganic acid such ashydrochloric acid, hydrobromic acid, sulfuric acid, nitric acid,phosphoric acid and heteropoly acid; an organic acid such as oxalicacid, trifluoroacetic acid, methanesulfonic acid, benzenesulfonic acid,p-toluenesulfonic acid and trifluoromethanesulfonic acid; and a Lewisacid such as aluminum trichloride, aluminum ethoxide, aluminumisopropoxide, boron trifluoride, boron trichloride, boron tribromide,tin tetrachloride, tin tetrabromide, dibutyltin dichloride, dibutyltindimethoxide, dibutyltin oxide, titanium tetrachloride, titaniumtetrabromide, titanium(IV) methoxide, titanium(IV) ethoxide,titanium(IV) isopropoxide and titanium(IV) oxide. The base catalyst tobe used may be mentioned an inorganic base such as sodium hydroxide,potassium hydroxide, barium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, lithium hydride, sodium hydride,potassium hydride and calcium hydride; an alkyl metal such as methyllithium, n-butyl lithium, methylmagnesium chloride and ethylmagnesiumbromide; an alkoxide such as sodium methoxide, sodium ethoxide andpotassium t-butoxide; and an organic base such as triethylamine,diisopropylethylamine, N,N-dimethylaniline, pyridine and4-dimethylaminopyridine. A reaction temperature is preferably from −50°C. to the boiling point of the solvent, more preferably room temperatureto 100° C.

Here, for leading from (13) to (8) by the dehydration condensationreaction, when L₁ in (13) is, for example, a group having a carbon atomsubstituted by one or more hydrogen atoms at the terminal such as apolymethylene group, etc., (in the following (13′), L₃ represents alinear, branched or cyclic divalent hydrocarbon group having 1 to 28carbon atoms, and the methylene group constituting L₃ may be substitutedby an oxygen atom or a carbonyl group.), an intramolecular dehydrationreaction proceeds to produce a by-product(s) (14) and (15) so that theobjective composition (8) cannot be obtained with good yield.

In the intermediate product (11) in which the ring structure Ar3 isintroduced, it is preferred since an intramolecular dehydration reactionin the intermediate product does not occur whereby the objectivecomposition (7) can be obtained with good yield.

The compound represented by the formula (1) may be exemplified by thefollowing, but the invention is not limited by these.

For using the organic film composition obtained by the present inventionas a resist underlayer film or a planarizing composition formanufacturing a semiconductor apparatus, the compound represented by theformula (iii) may be polymerized, if necessary, to prepare a compoundhaving a partial structure represented by the following formula (iv),

wherein R¹ represents a linear, branched or cyclic monovalenthydrocarbon group having 1 to 20 carbon atoms, and the methylene groupconstituting R¹ may be substituted by an oxygen atom; each c, d, c′ andd′ represent independently 0, 1 or 2; x and y each independentlyrepresent 0 or 1, when x=0, then c=0, and when y=0, then c′=0; Lrepresents a partial structure represented by the formula (ii); L₂represents a linear, branched or cyclic divalent organic group having 2to 30 carbon atoms; and the methylene group constituting L₂ may besubstituted by an oxygen atom or a carbonyl group, and the hydrogen atomconstituting the structure may be substituted by a hydroxyl group.

As a preferred form of the partial structure represented by the formula(iv), a partial structure represented by the following formula (2) maybe mentioned,

wherein the ring structures Ar1, Ar2 and Ar3 each represent asubstituted or unsubstituted benzene ring or naphthalene ring; R¹represents a linear, branched or cyclic monovalent hydrocarbon grouphaving 1 to 20 carbon atoms, and the methylene group constituting R¹ maybe substituted by an oxygen atom; each c, d, c′ and d′ representindependently 0, 1 or 2; x and y each independently represent 0 or 1,when x=0, then c=0, and when y=0, then c′=0; e is 0 or 1; L₁ representsa linear, branched or cyclic divalent hydrocarbon group having 2 to 30carbon atoms containing an aliphatic hydrocarbon group; L₂ represents alinear, branched or cyclic divalent hydrocarbon group having 2 to 30carbon atoms, and the methylene group constituting L₁ and L₂ may besubstituted by an oxygen atom or a carbonyl group, and the hydrogen atomconstituting L₂ may be substituted by a hydroxyl group.

The L₂ is a linear, branched or cyclic divalent hydrocarbon group having2 to 30 carbon atoms, and the divalent hydrocarbon group may bespecifically exemplified by the following.

CH₂₂ CH₂₃ CH₂₄ CH₂₅ CH₂₆ CH₂₇ CH₂₈ CH₂₉ CH₂₁₀ CH₂₁₁CH₂₁₂ CH₂₁₃ CH₂₁₄ CH₂₁₅ CH₂₁₆ CH₂₁₇ CH₂₁₈ CH₂₁₉ CH₂₂₀CH₂₂₁ CH₂₂₂ CH₂₂₃ CH₂₂₄ CH₂₂₅ CH₂₂₆ CH₂₂₇ CH₂₂₈ CH₂₂₉CH₂₃₀—CH₂₂O— —CH₂₃O— —CH₂₄O— —CH₂₅O— —CH₂₆O— —CH₂₇O— —CH₂₈O——CH₂₉O— —CH₂₁₀O— —CH₂₁₁O— —CH₂₁₂O— —CH₂₁₃O— —CH₂₁₄O——CH₂₁₅O— —CH₂₁₆O— —CH₂₁₇O— —CH₂₁₈O— —CH₂₁₉O— —CH₂₂₀O——CH₂₃₀O——OCH₂—CH₂—O₃ —OCH₂—CH₂—O₄ —OCH₂—CH₂—O₅ —OCH₂—CH₂—O₆—OCH₂—CH₂—O₇ —OCH₂—CH₂—O₈ —OCH₂—CH₂—O₉ —OCH₂—CH₂—O₁₀—OCH₂—CH₂—O₁₁ —OCH₂—CH₂—O₁₂ —OCH₂—CH₂—O₁₃ —OCH₂—CH₂—O₁₄—OCH₂—CH₂—O₁₅—OCH₃H₆—O —OCH₃H₆—O₂ —OCH₃H₆—O₃ —OCH₃H₆—O₄ —OCH₃H₆—O₅—OCH₃H₆—O₆ —OCH₃H₆—O₇ —OCH₃H₆—O₈ —OCH₃H₆—O₉ —OCH₃H₆—O₁₀

In addition, there may be exemplified by a group in which two hydrogenatoms are removed from a hydrocarbon group such as propylene, n-butane,1-butene, 2-butene, isobutane, n-pentane, n-hexane, n-heptane, n-octane,n-nonane, n-decane, n-dodecane, n-eicosane, 1,4-dimethylcyclohexane,1,3-dimethyladamantane, o-xylene, m-xylene, p-xylene,1,4-dimethylnaphthalene, 1,5-dimethylnaphthalene,2,6-dimethylnaphthalene and 2,7-dimethylnaphthalene.

Examples of making a higher molecular weight of the compound representedby the formula (iii),

P1) condensation reaction with an organic halogen compound andP2) condensation reaction with a polyolare mentioned and explained.P1) Condensation Reaction with an Organic Halogen Compound

The condensation reaction of the compound represented by the formula(iii) and an organic halogen compound is generally carried out in theabsence of a solvent or in a solvent, at room temperature, or undercooling or under heating, if necessary.

The organic halogen compound may be specifically exemplified by adihaloalkane such as 1,2-dichloroethane, 1,2-dibromoethane,1,3-dichloropropane, 1,3-dibromopropane, 1,3-diiodopropane,1,4-dichlorobutane, 1,4-dibromobutane, 1-bromo-4-chlorobutane,1,4-diiodobutane, 1,5-dichloropentane, 1,5-dibromopentane,1,5-diiodopentane, 1,6-dichlorohexane, 1,6-dibromohexane,1-bromo-6-chloro-hexane, 1,6-diiodohexane, α,α′-dibromo-m-xylene,α,α′-dibromo-o-xylene, α,α′-dibromo-p-xylene,2,5-bromomethylnaphthalene, 2,6-bromomethylnaphthalene,2,7-bromomethylnaphthalene and 1,8-bromomethylnaphthalene; and anepihalohydrin such as epifluorohydrin, epichlorohydrin, epibromohydrin,epiiodohydrin and β-methylepichlorohydrin, but the invention is notlimited by these. These organic halogen compounds may be used alone ormay be used in combination of two or more kinds.

An amount of the organic halogen compound to be used is preferably 0.05to 5 mol, more preferably 0.1 to 1.5 mol based on 1 mol of the compoundrepresented by the formula (iii).

The condensation reaction with the organic halogen compound ispreferably carried out under basic conditions. The base to be used maybe exemplified by an inorganic base such as sodium hydroxide, potassiumhydroxide, barium hydroxide, sodium carbonate, sodium hydrogencarbonate, potassium carbonate, lithium hydride, sodium hydride,potassium hydride and calcium hydride; an alkyl metal such as methyllithium, n-butyl lithium, methylmagnesium chloride and ethylmagnesiumbromide; an alkoxide such as sodium methoxide, sodium ethoxide andpotassium t-butoxide; and an organic base such as triethylamine,diisopropylethylamine, N,N-dimethylaniline, pyridine and4-dimethylaminopyridine. An amount of the base to be used is preferably1.0 to 5.0 mol, more preferably 2.0 to 3.0 mol based on 1 mol of thecompound represented by the formula (iii). As the method of thereaction, the compound represented by the formula (iii), the organichalogen compound and a base are charged at once, or a method in which anoptional component is added dropwise. The base or metal impurities canbe removed by the usual aqueous post-treatment. As others, by adding apoor solvent and separating the poor solvent layer, startingcomposition(s) or low molecular weight polymer fraction(s) can beremoved. Moreover, if necessary, an amount of the metal impurities canbe reduced by passing through a metal-removing filter. Thesepurification treatments may be carried out singly or may be carried outin combination of two or more kinds.

The solvent to be used in the condensation reaction may be exemplifiedby an ether such as diethyl ether, dibutyl ether, diethylene glycoldiethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and1,4-dioxane; a chlorine solvent such as methylene chloride, chloroform,dichloroethane and trichloroethylene; a hydrocarbon such as hexane,heptane, benzene, toluene, xylene and cumene; a nitrile such asacetonitrile; a ketone such as acetone, ethyl methyl ketone and isobutylmethyl ketone; an ester such as ethyl acetate, n-butyl acetate andpropylene glycol methyl ether acetate; and an aprotic polar solvent suchas dimethylsulfoxide, N,N-dimethylformamide, hexamethylphosphorictriamide and N-methyl-2-pyrrolidone, and these may be used alone or maybe used in combination of two or more kinds. The reaction may be carriedout by two-layer using the organic solvent and water, and in this case,to proceed the reaction rapidly, there may be added a phase-transfercatalyst such as tetramethylammonium chloride, tetraethylammoniumbromide, tetraethylammonium chloride, tetrapropylammonium bromide,tetrapropylammonium hydroxide, tetrabutylammonium bromide,tetrabutylammonium hydroxide, tetrabutylammonium hydrogen sulfate,tributylmethylammonium chloride, trioctylmethylammonium chloride,trilaurylmethylammonium chloride, benzyltrimethylammonium chloride,benzyltrimethylammonium hydroxide, benzyltriethylammonium chloride,benzyltributylammonium chloride and phenyltrimethylammonium chloride.

A reaction temperature of the condensation reaction is preferably from−50° C. to the boiling point of the solvent, more preferably roomtemperature to 150° C.

At the time of the condensation reaction of the compound represented bythe formula (iii), co-condensation may be carried out by co-presentingother phenol compound(s) having a plural number of phenolic hydroxylgroups. The phenol compound capable of carrying out the co-condensationmay be mentioned resorcinol, 2-methylresorcinol, 4-methylresorcinol,5-methylresorcinol, catechol, hydroquinone, 4-t-butylcatechol,1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene,1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene,2,7-dihydroxynaphthalene, bisphenol, 9,9-bis(4-hydroxyphenyl)fluorene,9,9-bis(6-hydroxy-2-naphthyl)fluorene and trisphenol. Also, the hydrogenatom(s) in these compounds may be substituted by a halogen atom, ahydrocarbon group, a hydroxyl group, an alkoxy group, a nitro group, anda cyano group.

Incidentally, there is a case that the compound having a partialstructure represented by the formula (iv) when e=1, there can besynthesized bypassing the condensation reaction of the compoundrepresented by the formula (iii). That is, a compound represented by theformula (3a) mentioned below and the organic halogen compound arereacted under the basic conditions to obtain a compound wherein L₁ andL₂ in the formula (iv) are the same. Examples of the compoundrepresented by the formula (3a) are mentioned below. At this time, anamount of the organic halogen compound to be used is preferably 0.1 to10 mol, more preferably 0.3 to 5 mol based on 1 mol of (3a).

P2) Condensation Reaction with a Polyol

The condensation reaction of the compound represented by the formula(iii) with a polyol is generally carried out in the absence of a solventor in a solvent, at room temperature, or under cooling or under heating,if necessary.

The polyol may be specifically exemplified by ethylene glycol,polyethylene glycol such as diethylene glycol, triethylene glycol,tetraethylene glycol, pentaethylene glycol and hexaethylene glycol;propylene glycol and glycerin, but the invention is not limited bythese. These polyols may be used alone or may be used in combination oftwo or more kinds.

An amount of the polyol to be used is preferably 0.1 to 10.0 mol, morepreferably 0.3 to 5.0 mol based on 1 mol of the compound represented bythe formula (iii).

In the condensation reaction, a catalyst may be used. An acid catalystis particularly preferred. The acid catalyst which can be used may bementioned an inorganic acid such as hydrochloric acid, hydrobromic acid,nitric acid, sulfuric acid, formic acid, phosphoric acid and heteropolyacid; an organic acid such as oxalic acid, acetic acid, trifluoroaceticacid, methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acidand trifluoromethanesulfonic acid; and a Lewis acid such as aluminumtrichloride, aluminum ethoxide, aluminum isopropoxide, borontrifluoride, boron trichloride, boron tribromide, tin tetrachloride, tintetrabromide, dibutyltin dichloride, dibutyltin dimethoxide, dibutyltinoxide, titanium tetrachloride, titanium tetrabromide, titanium(IV)methoxide, titanium(IV) ethoxide, titanium(IV) isopropoxide andtitanium(IV) oxide. More specifically, there may be mentioned an acidcatalyst such as hydrochloric acid, nitric acid, sulfuric acid, formicacid, oxalic acid, acetic acid, methanesulfonic acid, camphorsulfonicacid, p-toluenesulfonic acid and trifluoromethanesulfonic acid. Anamount of these acid catalysts to be used is 0.1 to 50.0 mol based on 1mol of the compound represented by the formula (iii). As the method ofthe reaction, there is a method in which the compound represented by theformula (iii), a polyol and a catalyst are charged at once, or a methodin which an optional component is added dropwise. After completion ofthe reaction, to remove unreacted starting composition(s) or a catalystexisting in the reaction system, a temperature of the reaction vessel israised to 130 to 230° C., and a volatile component(s) can be removed at1 to 50 mmHg. The catalyst or metal impurities can be removed by theusual aqueous post-treatment. As others, by adding a poor solvent andseparating the poor solvent layer, starting composition(s) or lowmolecular weight polymer fraction(s) can be removed. Moreover, ifnecessary, an amount of the metal impurities can be reduced by passingthrough a metal-removing filter. These purification treatments may becarried out singly or may be carried out in combination of two or morekinds.

The solvent to be used in the condensation reaction may be exemplifiedby an alcohol such as methanol, ethanol, isopropyl alcohol, butanol,ethylene glycol, propylene glycol, diethylene glycol and glycerol; anether such as ethylene glycol monomethyl ether, propylene glycolmonomethyl ether, diethyl ether, dibutyl ether, diethylene glycoldiethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and1,4-dioxane; a chlorine solvent such as methylene chloride, chloroform,dichloroethane and trichloroethylene; a hydrocarbon such as hexane,heptane, benzene, toluene, xylene and cumene; a nitrile such asacetonitrile; a ketone such as acetone, ethyl methyl ketone and isobutylmethyl ketone; an ester such as ethyl acetate, n-butyl acetate andpropylene glycol methyl ether acetate; and an aprotic polar solvent suchas dimethylsulfoxide, N,N-dimethylformamide and hexamethylphosphorictriamide, and these may be used alone or may be used in combination oftwo or more kinds.

A reaction temperature of the condensation reaction is preferably from−50° C. to the boiling point of the solvent, more preferably roomtemperature to 150° C.

At the time of the condensation reaction of the compound represented bythe formula (iii), co-condensation may be carried out by co-presentingother phenol compound(s) having a plural number of phenolic hydroxylgroups. The phenol compound capable of carrying out the co-condensationmay be mentioned resorcinol, 2-methylresorcinol, 4-methylresorcinol,5-methylresorcinol, catechol, hydroquinone, 4-t-butylcatechol,1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene,1,7-dihydroxynaphthalene, 2,6-dihydroxynaphthalene,2,7-dihydroxynaphthalene, bisphenol, 9,9-bis(4-hydroxyphenyl)fluorene,9,9-bis(6-hydroxy-2-naphthyl)fluorene and trisphenol. Also, the hydrogenatom(s) in these compounds may be substituted by a halogen atom, ahydrocarbon group, a hydroxyl group, an alkoxy group, a nitro group, anda cyano group.

Also, into the phenol structure and naphthol structure of the compoundrepresented by the formula (iii) or the compound having a partialstructure represented by the formula (iv) may be introduced an aromaticor alicyclic substituent. Here, the substituent which can be introducedmay be specifically mentioned as follows.

Among the substituents, for exposure at 248 nm, a polycyclic aromaticgroup, for example, an anthracenemethyl group and a pyrenemethyl groupare most preferably used. To improve transparency at 193 nm, thosehaving an alicyclic structure or those having a naphthalene structureare preferably used. The introducing method of the substituent may bementioned a method in which an alcohol compound which the bondingposition of the substituent is a hydroxyl group is introduced into thecompound represented by the formula (iii) or the compound having apartial structure represented by the formula (iv) in the presence of anacid catalyst. Examples of the acid catalyst may be mentioned the sameone as the acid catalyst mentioned in the condensation reaction (P2) ofthe polyol.

A molecular weight of the compound having the partial structurerepresented by the formula (iv) is preferably a weight average molecularweight (Mw) in terms of a polystyrene according to gel permeationchromatography (GPC) using tetrahydrofuran as a solvent of 400 to100,000, particularly preferably 500 to 10,000. A molecular weightdistribution in the range of 1.2 to 7 is preferably used. When a monomercomponent, an oligomer component or a low molecular weight componenthaving a molecular weight (Mw) of less than 1,000 is cut to narrow themolecular weight distribution, cross-linking efficiency becomes high.Also, by restraining an amount of the volatile component during thebaking, contamination at the peripheral of the baking cup can beprevented.

Also, in the present invention, as those having the partial structurerepresented by the formula (ii), a polymer compound having at least oneof a partial structure represented by the following formula (v), apartial structure represented by the following formula (vi), and apartial structure represented by the following formula (vii) can beused.

wherein R¹, a, b, a′, b′, c, d, c′, d′, x, y and L have the samemeanings as defined above; L₃ represents a linear, branched or cyclicdivalent organic group having 1 to 20 carbon atoms, L₄ represents L₃, apartial structure represented by the formula (i), or a partial structurerepresented by the formula (ii); 0≦i≦1, 0≦j≦1 and i+j=1.

wherein Ar1, Ar2, R¹, a, b, a′, b′, c, d, c′, d′, x and y have the samemeanings as defined above; L₅ represents a linear, branched or cyclicdivalent organic group having 1 to 20 carbon atoms, L₆ represents apartial structure represented by the formula (i) or a partial structurerepresented by the formula (ii); 0≦m<1, 0<n≦1 and m+n=1.

wherein R¹, a, b, c, d and x have the same meanings as defined above; L₇represents a linear, branched or cyclic divalent organic group having 1to 20 carbon atoms, L₈ represents a partial structure represented by theformula (i) or a partial structure represented by the formula (ii);0≦o<1, 0<p≦1 and o+p=1.

The organic group represented by L₃, L₅ or L₇ in the formulae may beexemplified by the following.

Of these, the partial structure represented by the formula (v) can beobtained by reacting the compound represented by the formula (ii)mentioned above with Compound (11) or Compound (13) which is a reactionintermediate. At this time, A-CHO is further reacted with Compound (10)to obtain a compound represented by the formula (v). The reactionconditions are the same as the conditions of obtaining (D) the resincontaining an aromatic ring as mentioned below.

Also, the present invention provides an organic film composition whichuses one or more of (A) the compound represented by the formula (iii),(B) the compound having the partial structure represented by the formula(iv), (C-1) the polymer compound having the partial structurerepresented by the formula (iv) as a part of the repeating unit, (C-2)the polymer compound having the partial structure represented by theformula (v), (C-3) the polymer compound having the partial structurerepresented by the formula (vi), and (C-4) the polymer compound havingthe partial structure represented by the formula (vii). The organic filmcomposition can be used for the use of a resist underlayer filmcomposition or a planarizing composition for manufacturing asemiconductor apparatus.

The organic film composition may further contain (D) a resin containingan aromatic ring which is different from the (C-1) to (C-4).

The resin (D) containing an aromatic ring which can be formulated intothe organic film composition is not specifically limited so long as itis a resin satisfying a film-forming property by spin coating andcurability, and it is more preferred to contain a naphthalene ring inthe view points of etching resistance, optical characteristic and heatresistance.

As (D) the resin containing an aromatic ring suitably formulated withthe organic film composition, more specifically, there may be preferablymentioned those containing a resin obtained by polycondensating one ortwo or more kinds of the following aromatic ring-containing compounds,and a compound represented by the below mentioned formula (4) underacidic or basic conditions, in addition to (D-1) and (D-2) mentionedhereinbelow. In the following formulae, Me represents a methyl group,and hereinafter the same.

As (D) the resin containing an aromatic ring to be formulated into theorganic film composition, more specifically, there may be preferablymentioned those containing a resin (D-1) obtained by polycondensatingeither one or more of the compound(s) represented by the followingformulae (3a) and (3b), and a compound represented by the belowmentioned formula (4),

wherein each R² each independently represent a hydrogen atom or asaturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms;each R³ independently represent a benzene ring or a naphthalene ring;each m1+m2, m3+m4 and m5+m6 represent 1 or 2; and each n1, n2 and n3represent 0 or 1,

A-CHO  (4)

wherein A represents either one of a hydrogen atom, a hydrocarbon grouphaving 1 to 10 carbon atoms and a substituted or unsubstituted aromatichydrocarbon group having 6 to 20 carbon atoms.

The compound represented by the formula (3a) may be specificallyexemplified as follows.

The compound contains a cardo structure of quaternary carbon, whereby itcontains an extremely high heat resistance. When an inorganic hard maskmiddle layer film such as a silicon oxide film, a silicon nitride filmand a silicon oxynitride film on a resist underlayer film or aplanarizing film for manufacturing a semiconductor apparatus by CVD orthe like, high temperatures exceeding 300° C. are required particularlyin the case of nitride based films, and it can be suitably used for sucha use.

The compound represented by the formula (3b) may be specificallyexemplified as follows. In the following formulae, Ph represents aphenyl group, and hereinafter the same.

The polycondensation resin using the compound as a starting compositionis excellent in thermosetting property, and dense and hard film can beformed after film formation, so that deformation at etching and heattreatment can be inhibited, and it is suitably used for various kinds offine processing as an underlayer or a planarizing film.

The compound (aldehydes) represented by the formula (4) may bementioned, for example, formaldehyde, acrolein, benzaldehyde,acetaldehyde, propionaldehyde, phenylacetaldehyde,α-phenylpropionaldehyde, β-phenylpropionaldehyde, o-hydroxybenzaldehyde,m-hydroxybenzaldehyde, p-hydroxybenzaldehyde, o-chlorobenzaldehyde,m-chlorobenzaldehyde, p-chlorobenzaldehyde, o-nitrobenzaldehyde,m-nitrobenzaldehyde, p-nitrobenzaldehyde, o-methylbenzaldehyde,m-methylbenzaldehyde, p-methylbenzaldehyde, p-ethylbenzaldehyde,p-n-butylbenzaldehyde, 1-naphthoaldehyde, 2-naphthoaldehyde,6-hydroxy-2-naphthoaldehyde, 1-hydroxy-2-naphthoaldehyde and furfural,preferably formaldehyde, benzaldehyde, 1-naphthoaldehyde and2-naphthoaldehyde.

In this case, formaldehyde can be particularly suitably used. Also,these aldehydes can be used alone or in combination of two or morekinds. An amount of the aldehydes to be used is preferably 0.2 to 5 mol,more preferably 0.5 to 2 mol based on 1 mol of the compound representedby the formulae (3a) and (3b).

As a supplying form when formaldehyde is to be used, in addition to anaqueous formaldehyde solution generally used, any compounds can be usedso long as it shows the same reactivity as that of the formaldehydeduring the polycondensation reaction such as paraformaldehyde,hexamethylenetetraamine, 1,3,5-trioxane, and an acetal such asformaldehyde dimethyl acetal.

Also, the resin (D-1) can be obtained by polycondensating either one ormore of the compound(s) represented by the formulae (3a) and (3b), andthe compound represented by the formula (4) by using an acid catalyst ora base catalyst.

The acid catalyst which can be used may be mentioned an organic acid ora mineral acid such as hydrochloric acid, nitric acid, sulfuric acid,formic acid, oxalic acid, acetic acid, methanesulfonic acid,camphorsulfonic acid, tosylic acid, trifluoromethanesulfonic acid andphosphoric acid. An amount of these acid catalysts to be used ispreferably 1×10⁻⁵ to 5×10⁻¹ mol based on 1 mol of the compoundrepresented by the formula (3a) and (3b).

The base catalyst may be specifically mentioned an inorganic base or anorganic base such as potassium hydroxide, sodium hydroxide, lithiumhydroxide, barium hydroxide, calcium hydroxide, potassium carbonate,sodium carbonate, tetramethylammonium hydroxide, aqueous ammonia anddiazabicycloundecene (DBU). An amount of these base catalysts to be usedis preferably 1×10⁻³ to 1×10 mol based on 1 mol of the compoundrepresented by the formula (3a) and (3b).

The reaction solvent in the polycondensation of the compound representedby the formula (3a) and (3b) may be mentioned, for example, water,methanol, ethanol, propanol, butanol, isopropyl alcohol,tetrahydrofuran, dioxane, toluene, xylene, methylene chloride,dichloroethane, methyl cellosolve, methoxypropyl acetate,γ-butyrolactone, butyl cellosolve, propylene glycol monomethyl ether, ora mixed solvent thereof. These solvents are preferably used in the rangeof 0 to 5,000 parts by mass based on 100 parts by mass of the startingcompositions of the reaction.

A reaction temperature in the polycondensation may be optionallyselected depending on the reactivity of the reaction startingcomposition(s), and generally in the range of 0 to 200° C.

As the method of the polycondensation, there may be mentioned a methodin which either one or more of the compound(s) represented by theformulae (3a) and (3b), the compound represented by the formula (4), anda reaction catalyst are charged at once, or a method in which either oneor more of the compound(s) represented by the formulae (3a) and (3b),and the compound represented by the formula (4) are added dropwise inthe presence of a reaction catalyst.

After completion of the polycondensation reaction, to remove unreactedstarting composition(s) or reaction catalyst existing in the reactionsystem, a temperature of the reaction vessel is raised to 130 to 230°C., and volatile component(s) may be removed under 1 to 50 mmHg, ifnecessary. The catalyst or metal impurities can be removed by the usualaqueous post-treatment. As others, by adding a poor solvent andseparating the poor solvent layer, starting composition(s) or lowmolecular weight polymer fraction(s) can be removed. Moreover, ifnecessary, an amount of the metal impurities can be reduced by passingthrough a metal-removing filter. These purification treatments may becarried out singly or may be carried out in combination of two or morekinds.

The compound(s) represented by the formulae (3a) and (3b) may bepolymerized alone, or may be used two or more kinds in combination withthe other compound(s) represented by the formulae (3a) and (3b).

A molecular weight of the resin (D-1) obtained by the polycondensationin terms of a polystyrene is a weight average molecular weight (Mw) of1,000 to 30,000, particularly preferably 1,500 to 20,000. A molecularweight distribution in the range of 1.2 to 7 is preferably used.

When the organic film composition contains (D) the resin containing anaromatic ring which includes such a resin (D-1), the formed resistunderlayer film or the planarizing film for manufacturing asemiconductor apparatus is excellent in filling/planarizingcharacteristics to the substrate, and becomes a composition havingsolvent resistance and heat resistance.

As (D) the resin containing an aromatic ring, a resin (D-2) having 1 ormore repeating units represented by the following formula (5) is alsopreferably mentioned,

wherein each R⁴ independently represent a hydrogen atom or a saturatedor unsaturated hydrocarbon group having 1 to 20 carbon atoms; R⁵represents a hydrogen atom or may form a ring by bonding with one of R⁴,and when R⁴ and R⁵ are bonded to form a ring, —R⁴—R⁵— represents asingle bond or an alkylene group having 1 to 3 carbon atoms; m7+m8represents 0, 1 or 2; and n4 represents 0 or 1.

The repeating unit represented by the formula (5) may be specificallyexemplified by the following.

The resin (D-2) having the repeating unit can be made a high carbondensity, so that it is excellent in etching resistance, wherebyparticularly suitably used for fine processing by etching.

Also, the resin (D-2) can be obtained by applying one or two or morekinds of a monomer(s) containing a polymerizable olefin compoundcorresponding to a repeating unit represented by the formula (5) or aprotected product thereof to addition polymerization, and deprotectingthe resulting product, if necessary. The addition polymerization can becarried out by the conventional manner such as radical polymerization,anion polymerization, and cation polymerization.

For example, in the case of the radical polymerizetion, it is generallycarried out by mixing a monomer(s) and a radical initiator in a solventor without solvent, and heating the mixture.

The radical initiator used may be mentioned an azo compound such asazobisisobutyronitrile and dimethyl azobisisobutyrate, and a peroxidesuch as benzoyl peroxide.

As a method of mixing, a suitable method can be selected depending onthe design of the polymer, and there may be mentioned, for example, amixing method in a lump, a method in which a monomer(s) and a radicalinitiator are mixed and the mixture is gradually added to a heatedsolvent, or a method in which a monomer(s) and a radical initiator areeach separately added to a heated solvent, and either of which methodcan be used in the present invention.

An amount of the radical initiator is preferably 1×10⁻⁵ to 5×10⁻¹ molbased on 1 mol of the monomer. Also, at the time of the polymerization,a chain transfer agent such as octanethiol, 3-mercaptopropionic acid and2-mercaptoethanol may be co-presented for the purpose of controlling themolecular weight or improving the yield.

The reaction solvent when a solvent is used in the radicalpolymerization may by mentioned, for example, water, methanol, ethanol,propanol, butanol, isopropyl alcohol, tetrahydrofuran, dioxane, toluene,xylene, methylene chloride, dichloroethane, methyl cellosolve,methoxypropyl acetate, γ-butyrolactone, butyl cellosolve, propyleneglycol monomethyl ether, 2-butanone, methyl isobutyl ketone,cyclohexanone, propylene glycol monomethyl ether acetate or a mixedsolvent thereof. An amount of these solvents is preferably in the rangeof 0 to 5,000 parts by mass based on 100 parts by mass of the startingcompositions. A reaction temperature may be optionally selecteddepending on reactivities of starting compositions and a decompositiontemperature of the initiator, and generally in the range of 0 to 100° C.

After completion of the polymerization reaction, impurities such as ametal can be removed by the usual aqueous post-treatment. By adding apoor solvent and subsequently separating the poor solvent layer,starting composition(s) or low molecular weight polymer fraction(s) canbe removed. Moreover, if necessary, an amount of the metal impuritiescan be reduced by passing through a metal-removing filter. Thesepurification treatments may be carried out singly or may be carried outin combination of two or more kinds.

The polymerizable olefin compound corresponding to a repeating unitrepresented by the formula (5) or a protected product thereof may bepolymerized alone, or may be polymerized two or more kinds, or may bepolymerized further in combination with the other known polymerizableolefin monomer(s).

A molecular weight of the resin (D-2) in terms of a polystyrene ispreferably a weight average molecular weight (Mw) of 1,000 to 100,000,particularly preferably 1,500 to 50,000. A molecular weight distributionthereof preferably used is in the range of 1.2 to 7.

As the other resins than (D) the resin containing an aromatic ring,resins described in paragraphs (0028) to (0029) of JP 2006-227391A canbe used.

Also, the organic film composition obtained by the present inventionpreferably contains (E) a compound containing a phenolic hydroxyl group,if necessary. Such (E) a compound containing a phenolic hydroxyl groupmay be preferably a compound represented by the formula (3a) or (3b).Also used are phenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol,2,5-dimethylphenol, 3,4-dimethylphenol, 3,5-dimethylphenol,2,4-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol,3,4,5-trimethylphenol, 2-t-butylphenol, 3-t-butylphenol,4-t-butylphenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol,3,5-diphenylphenol, 2-naphthylphenol, 3-naphthylphenol,4-naphthylphenol, 4-tritylphenol, resorcinol, 2-methylresorcinol,4-methylresorcinol, 5-methylresorcinol, catechol, 4-t-butylcatechol,2-methoxyphenol, 3-methoxyphenol, 2-propylphenol, 3-propylphenol,4-propylphenol, 2-isopropylphenol, 3-isopropylphenol, 4-isopropylphenol,2-methoxy-5-methylphenol, 2-t-butyl-5-methylphenol, pyrogallol, thymol,isothymol, 1-naphthol, 2-naphthol, 1-anthracenol, 1-pyrenol and9-phenanthrenol.

When the organic film composition contains (E) the compound containing aphenolic hydroxyl group, filling/planarizing characteristics can befurther improved in some cases.

Into the organic film composition, (F) an acid generator and (G) across-linking agent can be added to further promote a thermalcross-linking reaction.

In (F) the acid generators, there are one generating an acid by thermaldecomposition and one generating an acid by light irradiation, and anyone can be added. Specifically, compositions described in paragraphs(0061) to (0085) of JP 2007-199653A can be added.

As (G) the cross-linking agent usable for the organic film composition,compositions described in paragraphs (0055) to (0060) of JP 2007-199653Acan be added.

Further, into the organic film composition, (H) a surfactant can beadded to improve coatability in spin coating. The surfactant can be usedthose described in paragraphs (0142) to (0147) of JP 2009-269953A.

As (I) an organic solvent usable in the organic film composition, it isnot specifically limited so long as it can dissolve the compoundrepresented by the formula (1) of Component (A), the compound having apartial structure represented by the formula (2) of Component (B), thepolymer compound containing the compound of the formula (2) as a part ofthe repeating unit of Component (C), and the resin containing anaromatic ring (D), and those which can also dissolve (E) a compoundcontaining a phenolic hydroxyl group, (F) an acid generator, (G) across-linking agent and (H) a surfactant are preferred. Specifically,the solvents described in paragraphs (0091) to (0092) of JP 2007-199653Acan be added. Of these, propylene glycol monomethyl ether acetate,propylene glycol monomethyl ether, 2-heptanone, cyclopentanone,cyclohexanone, γ-butyrolactone, and a mixture of two or more kinds ofthese compositions are preferably used.

Furthermore, into the organic film composition, a basic compound can beblended to improve storage stability. The basic compound acts as aquencher to an acid to prevent trace of the acid generated from the acidgenerator from proceeding with a cross-linking reaction. Specifically,compositions described in paragraphs (0086) to (0090) of JP 2007-199653Acan be added as such a basic compound.

Also, into the organic film composition, an additive to further improvefilling/planarizing characteristics may be added in addition to thecompositions.

The additive is not particularly limited so long as it providesfilling/planarizing characteristics, and preferably used are, forexample, a liquid state additive having a polyethylene glycol orpolypropylene glycol structure, or, a thermo-decomposable polymer havinga weight loss ratio between 30° C. and 250° C. of 40% by mass or moreand a weight average molecular weight of 300 to 200,000. Thethermo-decomposable polymer preferably contains a repeating unit havingan acetal structure represented by the following formula (DP1) or (DP2):

wherein R⁶ represents a hydrogen atom or a saturated or unsaturatedmonovalent organic group having 1 to 30 carbon atoms which may besubstituted; and W represents a saturated or unsaturated divalentorganic group having 2 to 30 carbon atoms.

wherein R^(6a) represents an alkyl group having 1 to 4 carbon atoms;W^(a) represents a saturated or unsaturated divalent hydrocarbon grouphaving 4 to 10 carbon atoms, which may have an ether bond; and nrepresents an average repeating unit number and is 3 to 500.

In the process for forming an organic film, the organic film compositionis coated onto a substrate to be processed by a method such as spincoating method. Adopting the spin coating method, etc., allows forobtainment of an excellent filling property. After spin coating, bakingthereof is conducted in order to evaporate the solvent, to preventmixing of the composition with a resist upper layer film or a resistmiddle layer film, and to promote a cross-linking reaction. The bakingis conducted at a temperature in the range of 100° C. or higher and 600°C. or lower, for 10 to 600 seconds, preferably for 10 to 300 seconds.The baking temperature is more preferably 200° C. or higher and 500° C.or lower. In consideration of affections on device damage and waferdeformation, the upper limit of the heating temperature in a waferprocess of lithography is preferably 600° C. or lower, more preferably500° C. or lower.

Further, in the process for forming an organic film, the organic filmcomposition is coated on a substrate to be processed by a spin coatingmethod as mentioned above, and the composition is baked in an atmospherewith an oxygen concentration of 0.1% or more and 21% or less to becured, thereby forming an organic film.

The organic film composition is based in such an oxygen atmosphere,thereby enabling to obtain a fully cured film.

Baking atmosphere may be air, and inert gas such as N₂, Ar and He may befilled. Also, a baking temperature, etc., may be employed as mentionedabove.

Such a process for forming an organic film can provide a flat cured filmirrespective of unevenness of the substrate to be processed due to itsexcellent filling/planarizing characteristics, so that it is extremelyuseful for forming a flat cured film on a substrate having a structuralcomposition or step(s) with a height of 30 nm or more.

Incidentally, a thickness of the organic film such as the resistunderlayer film or the planarizing film for manufacturing asemiconductor apparatus can be optionally selected, and generally 30 to20,000 nm, particularly preferably 50 to 15,000 nm.

The organic film composition is extremely useful as a resist underlayerfilm composition of a multilayer resist process such as a two-layerresist process, a three-layer resist process using a silicon-containingmiddle layer film, and a four-layer resist process using asilicon-containing inorganic hard mask middle layer film and an organicantireflection film.

The present invention provides a patterning process which is a processfor forming a pattern on a substrate to be processed by using such aresist underlayer film composition, which comprises, at least, forming aresist underlayer film on a substrate to be processed by using theorganic film composition; forming a resist middle layer film compositionon the resist underlayer film by using a resist middle layer filmcomposition containing a silicon atom; forming a resist upper layer filmon the resist middle layer film by using a resist upper layer filmcomposition comprising a photoresist composition, to form a multilayerresist film; conducting exposure of a pattern circuit region of theresist upper layer film and then developing it by a developer to form aresist pattern on the resist upper layer film; etching the resist middlelayer film by using the pattern-formed resist upper layer film as anetching mask; etching the resist underlayer film by using thepattern-formed resist middle layer film as an etching mask; and etchingthe substrate to be processed by using the pattern-formed resistunderlayer film as an etching mask, to form a pattern on the substrateto be processed.

The silicon-containing resist middle layer of the three-layer resistprocess shows etching resistance to an oxygen gas or a hydrogen gas, sothat it is preferred to carry out the etching of the resist underlayerfilm using the resist middle layer film as a mask under an etching gasmainly comprising an oxygen gas or a hydrogen gas.

As the silicon-containing resist middle layer film in the three-layerresist process, a polysilsesquioxane-based middle layer film is alsopreferably used. This makes the resist middle layer film to possess anantireflective effect, thereby enabling to restrict reflection.Particularly, when a composition configured to contain many aromaticgroups so as to possess a higher resistance against substrate-etching isused as a resist underlayer film for 193 nm exposure, a k value israther increased to increase a substrate reflection. Nonetheless, thereflection is restricted by the resist middle layer film, therebyenabling to restrict the substrate reflection down to 0.5% or less.Preferably used as the resist middle layer film having an antireflectiveeffect is a polysilsesquioxane, which has a pendant anthracene forexposure of 248 nm or 157 nm, or a pendant phenyl group or a pendantlight-absorbing group having a silicon-silicon bond for 193 nm exposure,and which is cross-linked by an acid or a heat.

In this case, formation of a silicon-containing resist middle layer filmby the spin coating method is easy and convenient than that by the CVDmethod so that it has a merit in a cost.

Further, an inorganic hard mask middle layer film may be formed as amiddle layer film. In this case, the process comprises the steps of, atleast, forming a resist underlayer film on the substrate to be processedby using the organic film composition; forming an inorganic hard maskmiddle layer film selected from any one of a silicon oxide film, asilicon nitride film and a silicon oxynitride film on the resistunderlayer film; forming a resist upper layer film on the inorganic hardmask middle layer film by using a resist upper layer film compositioncomprising a photoresist composition, to form a multilayer resist film;conducting exposure of a pattern circuit region of the resist upperlayer film and then developing it by a developer to form a resistpattern on the resist upper layer film; etching the inorganic hard maskmiddle layer film by using the obtained resist pattern as an etchingmask; etching the resist underlayer film by using the obtainedpattern-formed inorganic hard mask middle layer film as an etching mask;and etching the substrate to be processed by using the obtained resistunderlayer film as an etching mask, to form a pattern on the substrateto be processed.

As mentioned above, when the inorganic hard mask middle layer film isformed on the resist underlayer film, a silicon oxide film, a siliconnitride film and a silicon oxynitride film (SiON film) are formed by theCVD method or the ALD method. The method for forming a nitride film isdescribed in, for example, JP 2002-334869A and WO2004/066377. A filmthickness of the inorganic hard mask middle layer film is 5 to 200 nm,preferably 10 to 100 nm, and in particular, a SiON film which has higheffects as an antireflection film is most preferably used. A temperatureof the substrate in forming the SiON film is raised up to 300° C. to500° C., so that it is necessary to endure the temperature of 300° C. to500° C. as the underlayer. The organic film composition to be used inthe present invention has high heat resistance, and endures the hightemperature of 300° C. to 500° C., so that the inorganic hard maskformed by the CVD method or the ALD method, and the resist underlayerfilm formed by the spin coating method can be used in combination.

Further, the present invention can be suitably used for a four-layerresist process using an organic antireflection film. In this case, theprocess comprises the steps of, at least, forming a resist underlayerfilm on the substrate to be processed by using the organic filmcomposition; forming an inorganic hard mask middle layer film selectedfrom any one of a silicon oxide film, a silicon nitride film and asilicon oxynitride film on the resist underlayer film; forming anorganic antireflection film on the inorganic hard mask middle layerfilm; forming a resist upper layer film on the organic antireflectionfilm by using the resist upper layer film composition comprising aphotoresist composition, to form a multilayer resist film; conductingexposure of a pattern circuit region of the resist upper layer film andthen developing it by a developer to form a resist pattern on the resistupper layer film; etching the organic antireflection film and theinorganic hard mask middle layer film by using the obtained resistpattern as an etching mask; etching the resist underlayer film by usingthe obtained pattern-formed inorganic hard mask middle layer film as anetching mask; and etching the substrate to be processed by using theobtained pattern-formed resist underlayer film as an etching mask, toform a pattern on the substrate to be processed.

Although it may form a photoresist film on the inorganic hard maskmiddle layer film as a resist upper layer film as mentioned above, it isalso possible to form an organic antireflection film (BARC) on theinorganic hard mask middle layer film by spin coating, and a photoresistfilm may be formed thereon. In particular, when a SiON film is used asthe inorganic hard mask middle layer film, it is possible to restrictreflection by virtue of the two-layer antireflective films of the SiONfilm and the BARC film, even by a liquid immersion exposure at a higherNA exceeding 1.0. Another merit of the formation of the BARC resides inobtainment of an effect to reduce footing (trailing) of a photoresistpattern compared to a photoresist pattern just above the SiON film.

The resist upper layer film in the three-layer resist film may be apositive type or a negative type, and it is possible to use therefor thesame one as a typically used photoresist composition. When the monolayerresist upper layer film is formed by the photoresist composition, spincoating method is preferably used similarly to the case for forming theresist underlayer film. Prebaking is to be conducted after spin coatingof the photoresist composition, preferably at 60 to 180° C. for 10 to300 seconds. Thereafter, exposure is to be conducted according to ausual manner, followed by post-exposure baking (PEB) and development, tothereby obtain a resist pattern. Although a thickness of the resistupper layer film is not particularly limited, it is preferably 30 to 500nm, particularly preferably 50 to 400 nm.

Further, examples of light for exposure include high energy beams atwavelengths of 300 nm or shorter, specifically excimer lasers at 248 nm,193 nm, and 157 nm, soft X-rays at 3 to 20 nm, an electron beam, X-rays,and the like.

Next, etching is to be conducted by using the obtained resist pattern asa mask. In a three-layer process, etching of a resist middle layer filmor an inorganic hard mask middle layer film is to be conducted by usingthe resist pattern as a mask and by adopting a fluorocarbon-based gas.

Then, etching processing of the resist underlayer film is to beconducted by using the pattern-formed resist middle layer film or thepattern-formed inorganic hard mask middle layer film as a mask.

The subsequent etching of a substrate to be processed can be alsoconducted according to a usual manner, for example, the manner thatetching mainly based on a fluorocarbon-based gas is conducted when thesubstrate to be processed is made of SiO₂, SiN or silica-based lowdielectric constant insulating film, or etching mainly based on achlorine-based or bromine-based gas is conducted for a substrate made ofp-Si, Al or W. When substrate processing is conducted by etching by afluorocarbon-based gas, the silicon-containing middle layer of thethree-layer process is stripped simultaneously with the substrateprocessing. In the case of etching of a substrate by a chlorine-basedgas or a bromine-based gas, stripping of the silicon-containing middlelayer is required to be separately conducted by dry etching stripping bya fluorocarbon-based gas after the substrate processing.

The resist underlayer film is characterized in that the film isexcellent in etching resistance at the time of etching these substratesto be processed.

It is noted that the substrate to be processed is not particularlylimited, and a substrate made of Si, α-Si, p-Si, SiO₂, SiN, SiON, W, TiNor Al, or a composition in which a layer to be processed is formed onthe substrate may be used. Examples of the layer to be processed to beused include various Low-k films made of Si, SiO₂, SiON, SiN, p-Si,α-Si, W, W—Si, Al, Cu or Al—Si, and stopper films therefor, which caneach typically form into a thickness of 50 to 10,000 nm, particularly100 to 5,000 nm. When the layer to be processed is to be formed, thecomposition of the substrate to be used is different from those of thelayers to be processed.

An example of the three-layer resist process will be specificallyexplained by referring to FIGS. 1A-1F as follows.

In the case of the three-layer resist process, as shown in FIG. 1A, theprocess is configured to form a resist underlayer film 3 by using theorganic film composition on a layer to be processed 2 laminated on asubstrate 1, to thereafter form a resist middle layer film 4 thereon,and to form a resist upper layer film 5 thereon.

Next, as shown in FIG. 1B, exposure is conducted for required portions 6of the resist upper layer film, followed by PEB and development, to fora resist pattern 5 a (FIG. 1C). The thus obtained resist pattern 5 a isthen used as a mask, etching of the resist middle layer film 4 isconducted by using a CF-based gas to form a pattern-formed resist middlelayer film 4 a (FIG. 1D). After removing the resist pattern 5 a, theobtained pattern-formed resist middle layer film 4 a is used as a mask,etching of the resist underlayer film 3 is conducted by using an oxygenplasma to form a pattern-formed resist underlayer film 3 a (FIG. 1E).Further, after removing the pattern-formed resist middle layer film 4 a,the pattern-formed resist underlayer film 3 a is used as a mask, etchingof the layer to be processed 2 is conducted to form a pattern 2 a (FIG.1F).

When an inorganic hard mask middle layer film is used, the resist middlelayer film 4 is the inorganic hard mask middle layer film, and when aBARC is to be arranged, a BARC layer is provided between the resistmiddle layer film 4 and the resist upper layer film 5. Etching of theBARC may be continuously conducted prior to etching of the resist middlelayer film 4, or etching of the BARC alone may be conducted andsubsequently etching of the resist middle layer film 4 may be conductedby changing an etching apparatus.

EXAMPLES

In the following, the present invention is explained in more detail byreferring to Examples and Comparative Examples, but the presentinvention is not limited by these descriptions.

Incidentally, the measurement method of the molecular weight is carriedout specifically by the following mentioned method. A weight averagemolecular weight (Mw) and a number average molecular weight (Mn)calculated on a polystyrene using gel permeation chromatography (GPC)and tetrahydrofuran as an eluent were obtained and a polydispersity(Mw/Mn) was calculated.

Synthetic Example 1 Synthesis of Compound (I)

Under nitrogen atmosphere, in 1 L four-necked flask equipped with athermometer and a reflux condenser was prepared 300 ml of 0.67 mol/L1,4-tetramethylenebis(magnesium chloride)/tetrahydrofuran solution. Tothe solution was added dropwise 230.8 g of a tetrahydrofuran solutioncontaining 25 wt % of 9-fluorenone at an inner temperature of 40° C.,and after heating in an oil bath at 60° C. for 3 hours, the reaction wasstopped by adding 500 ml of a saturated aqueous ammonium chloridesolution. To the mixture were added 400 ml of pure water, 200 ml oftetrahydrofuran and 500 ml of hexane, and the resulting mixture wasstirred. At this time, the solution became yellowish white suspension.The suspension was collected by filtration using a Hirsch funnel, theprecipitated crystals were washed with pure water until the filtratebecame neutral, and then, washed twice with 300 ml ofhexane/tetrahydrofuran=4/1 (volume ratio). The resulting crystal wasvacuum dried at 60° C. to obtain 16.7 g of Compound (I) with a yield of24.9% and a GPC purity of 91.7%.

Compound (I):

IR (ATR method): ν=3288, 3065, 3039, 2933, 2861, 1608, 1586, 1466, 1447,1376, 1315, 1285, 1248, 1194, 1156, 1106, 1072, 1031, 952, 940, 829,777, 739, 732 cm⁻¹.

¹H-NMR (600 MHz in DMSO-d₆): δ=0.59 (4H, m), 1.77 (4H, m), 5.38 (2H,—OH), 7.22 (4H, t), 7.29 (4H, t), 7.35 (4H, d), 7.66 (4H, d) ppm.

¹³C-NMR (150 MHz in DMSO-d₆): δ=23.83, 39.63, 80.93, 119.69, 123.43,127.48, 128.09, 139.00, 149.62 ppm.

Synthetic Example 2 Synthesis of Compound (A1)

Under nitrogen atmosphere, to 300 mL three necked flask equipped with athermometer and a reflux condenser were added 10.0 g (23.9 mmol) ofCompound (I), 6.9 g (47.9 mmol) of 2-naphthol and 60 ml of1,2-dichloroethane, and the mixture was stirred in an oil bath at 30° C.to prepare a dispersion. To the dispersion was gradually added 3.0 ml ofmethanesulfonic acid, and the reaction was carried out in an oil bath at30° C. for 58 hours, and in an oil bath at 50° C. for 24 hours. Aftercooling to room temperature, 50 g of pure water was added to themixture, and insoluble composition was separated by filtration using aHirsch funnel. The filtrate was recovered and washed with 300 ml ofethyl acetate, and transferred to a separating funnel. Separating theliquids and washing with water were carried out until the aqueous layerbecame neutral, and then, the organic layer was evaporated by anevaporator to obtain yellow crystal. The obtained yellow crystal wasrecrystallized from 500 ml of hexane:1,2-dichloroethane=3:2 (volumeratio), collected by filtration using a Hirsch funnel, and furtherwashed twice with 200 ml of hexane:1,2-dichloroethane=2:1 (volumeratio). The crystal was recovered and vacuum dried at 60° C. to obtain4.4 g of Compound (A1) with a yield of 27.5% and a GPC purity of 89.4%.

Compound (A1):

IR (ATR method): ν=3527, 3056, 2932, 2856, 1704, 1634, 1603, 1506, 1475,1446, 1376, 1347, 1278, 1215, 1175, 1145, 1032, 952, 895, 861, 807, 769,754, 738 cm⁻¹.

¹H-NMR (600 MHz in DMSO-d₆): δ=0.49 (4H, m), 2.31 (4H, t), 6.58 (2H,d-d), 6.93 (2H, s-d), 6.98 (2H, d-d), 7.16 (4H, d), 7.22 (4H, t-d), 7.30(2H, d), 7.34 (4H, t-d), 7.64 (2H, d), 7.73 (s-d), 7.86 (4H, d), 9.60(2H, —OH) ppm.

¹³C-NMR (150 MHz in DMSO-d₆): δ=24.27, 36.62, 58.10, 108.15, 118.39,120.08, 123.90, 124.17, 125.75, 125.78, 127.19, 127.51, 127.65, 129.32,133.05, 138.86, 140.25, 151.28, 155.07 ppm.

TG-DTA (−5% weight loss temperature, in Air): 263° C.

TG-DTA (−5% weight loss temperature, in He): 282° C.

DSC (Glass transition temperature): 107° C.

Synthetic Example 3 Synthesis of Compound (II)

Under nitrogen atmosphere, in a 3 L four necked flask equipped with athermometer and a reflux condenser were weighed 300 g (1734.0 mmol) of4-bromophenol, 19.8 g (86.9 mmol) of benzyltriethylammonium chloride,333 g of 25% aqueous sodium hydroxide solution and 1000 ml oftetrahydrofuran, and the mixture was heated in an oil bath at 60° C. Tothe mixture was added dropwise 176.0 g (81.5 mmol) of 1,4-dibromobutanepreviously diluted with 100 g of tetrahydrofuran from a dropping funnelover 30 minutes, and the mixture was heated under reflux for 39 hours.The reaction mixture was diluted with 1000 ml of toluene, cooled to roomtemperature by allowing to stand and transferred to a separating funnel.The aqueous layer was disposed, the organic layer was further washedtwice with 500 g of 5% aqueous sodium hydroxide solution, and separationof the liquids and washing with water were repeated until the aqueouslayer became neutral. The organic layer was recovered and dried overanhydrous sodium sulfate, then, the drier was removed by filtration andthe solvent of the filtrate was removed by using an evaporator. Thecrystal obtained by evaporated to dryness was recovered and vacuum driedat 45° C. to obtain 306.7 g of compound (II) with a yield of 94.0% and aGPC purity of 99.2%.

Compound (II):

IR (ATR method): ν=3091, 2957, 2927, 2874, 1878, 1636, 1588, 1575, 1486,1466, 1445, 1408, 1387, 1316, 1299, 1287, 1240, 1199, 1170, 1116, 1102,1071, 1050, 1001, 975, 824, 804, 744 cm⁻¹.

¹H-NMR (600 MHz in CDCL3): δ=1.96 (4H, quint), 3.99 (4H, quint), 6.77(4H, d-t), 7.36 (4H, d-t) ppm.

¹³C-NMR (150 MHz in CDCL3): δ=25.86, 67.63, 112.76, 116.24, 132.23,158.02 ppm.

Synthetic Example 4 Synthesis of Compound (III)

Under nitrogen atmosphere, in a 2000 ml four necked flask equipped witha thermometer and a reflux condenser was weighed 38.0 g (95.0 mmol) ofCompound (II), 300 ml of tetrahydrofuran was added thereto to prepare auniform solution. The flask was cooled with acetonitrile-dry icerefrigerant, 80.4 ml of 2.6 mol/L n-butyl lithium-hexane solution wasadded dropwise to the solution from a dropping funnel over 30 minutesand then the mixture was stirred for 3 hours. Then, the refrigerant waschanged to an ice-cooling bath and 154.0 g of 20 wt %9-fluorenone-tetrahydrofuran solution was added dropwise to the mixturefrom a dropping funnel over 17 minutes. After stirring at roomtemperature for 4 hours, the reaction was stopped by adding 200 ml of asaturated aqueous ammonium chloride solution to the mixture. Thereaction mixture was diluted with 800 ml of ethyl acetate, transferredto a separating funnel and separation of liquids and washing with waterwere repeated until the aqueous layer became neutral. The organic layerwas recovered, and the solvent was removed by distillation until theinner composition in an evaporator became 510 g to obtain a suspension.To the obtained suspension was added dropwise 600 g of hexane understirring to precipitate crystals. The crystals were collected byfiltration using a Hirsch funnel, washed twice with 600 ml of ethylacetate:hexane=1/2 (volume ratio) and vacuum dried at 60° C. to obtain34.9 g of Compound (III) with a yield of 67.8% and a GPC purity of94.4%.

Compound (III):

IR (ATR method): ν=3381, 3174, 3053, 2955, 2861, 160, 1581, 1508, 1472,1448, 1413, 1381, 1292, 1243, 1166, 1114, 1097, 1011, 985, 947, 920,824, 774, 752, 736 cm⁻¹.

¹H-NMR (600 MHz in DMSO-d₆): δ=1.78 (4H, m), 3.92 (4H, m), 6.19 (2H,—OH), 6.73 (4H, d-t), 7.11 (4H, d-t), 7.20 to 7.22 (8H, m), 7.33 (4H,m), 7.78 (4H, d) ppm.

¹³C-NMR (150 MHz in DMSO-d₆): δ=25.38, 66.99, 82.22, 113.85, 120.00,124.57, 126.25, 127.95, 128.33, 136.88, 139.01, 151.47, 157.42 ppm.

Synthetic Example 5 Synthesis of Compound (A2)

Under nitrogen atmosphere, in a 1000 ml four necked flask equipped witha thermometer and a reflux condenser were weighed 50.0 g (83.0 mmol) ofCompound (III) and 78.1 g (829.9 mmol) of phenol, 400 ml of1,2-dichloroethane was added to the mixture to prepare a uniformsolution in an oil bath at 50° C. To the mixture was gradually addeddropwise 15.0 ml of methanesulfonic acid from a dropping funnel, and theresulting mixture was heated for 1 hour. After cooling the mixture toroom temperature by allowing to stand, the reaction mixture was dilutedwith 600 ml of methyl isobutyl ketone, transferred to a separatingfunnel, and separation of the liquids and washing with water wererepeated until the aqueous layer became neutral. The organic layer wasrecovered, and after removing the solvent by distillation until theinner composition in an evaporator became 150 g, 510 g of methanol wasadded dropwise to the mixture under stirring to precipitate crystals.The crystals were collected by filtration using a Hirsch funnel, washedtwice with 330 ml of methanol and vacuum dried at 60° C. to obtain 52.2g of Compound (A2) with a yield of 83.3% and a GPC purity of 92.7%.

Compound (A2):

IR (ATR method): ν=3403, 3033, 2950, 2871, 1609, 1506, 1472, 1446, 1293,1243, 1175, 1106, 1049, 1013, 971, 915, 821, 747, 729 cm⁻¹.

¹H-NMR (600 MHz in DMSO-d₆): δ=1.76 (4H, m), 3.90 (4H, m), 6.62 (4H,d-t), 6.75 (4H, d-t), 6.89 (4H, d-t), 6.96 (4H, d-t), 7.26 (4H, t-d),7.34 (8H, m), 7.87 (4H, d), 9.30 (2H, —OH) ppm.

¹³C-NMR (150 MHz in DMSO-d₆): δ=25.35, 63.55, 66.94, 114.06, 114.92,120.33, 125.85, 127.30, 127.66, 128.59, 128.63, 135.67, 137.68, 139.29,151.44, 156.00, 157.20 ppm.

TG-DTA (−5% weight loss temperature, in Air): 348° C.

TG-DTA (−5% weight loss temperature, in He): 339° C.

DSC (Glass transition temperature): 112° C.

Synthetic Example 6 Synthesis of Compound (A3)

Under nitrogen atmosphere, in a 1000 ml four necked flask equipped witha thermometer and a reflux condenser were weighed 50.0 g (83.0 mmol) ofCompound (III) and 95.7 g (663.7 mmol) of 2-naphthol, and 550 ml of1,2-dichloroethane was added to the mixture to prepare a uniformsolution in an oil bath at 50° C. To the mixture was gradually addeddropwise 2.6 ml of methanesulfonic acid from a dropping funnel, and themixture was heated for 2 hours. After cooling the mixture to roomtemperature by allowing to stand, the reaction mixture was diluted with1000 ml of methyl isobutyl ketone, transferred to a separating funnel,and separation of the liquids and washing with water were repeated untilthe aqueous layer became neutral. The organic layer was recovered, andafter removing the solvent by distillation until the inner compositionin an evaporator became 160 g, 300 g of methanol was added to theresidue. The mixture was heated to 60° C. to prepare a uniform solution,30 g of pure water was added to the solution under stirring, andstirring at room temperature was continued to precipitate a ricecake-like lump. The supernatant was removed by decantation and theprecipitate was recrystallized from 1800 g of isopropylalcohol:water=7:3 (weight ratio). The crystals were collected byfiltration using a Hirsch funnel, washed twice with 380 g of isopropylalcohol:water 1:3 (weight ratio) and vacuum dried at 60° C. to obtain46.6 g of Compound (A3) with a yield of 65.7% and a GPC purity of 85.2%.

Compound (A3):

IR (ATR method): ν=3526, 3055, 2964, 1634, 1605, 1578, 1504, 1474, 1446,1390, 1289, 1277, 1245, 1179, 1120, 1013, 979, 959, 945, 898, 860, 829,812, 752, 738 cm⁻¹.

¹H-NMR (600 MHz in DMSO-d₆): δ=1.77 (4H, m), 3.92 (4H, m), 6.77 (4H,d-t), 6.99 (2H, d-d), 7.02 (4H, m), 7.04 (2H, s-d), 7.19 (2H, d-d), 7.28(4H, t), 7.34 to 7.38 (6H, m), 7.44 (2H, d), 7.52 (2H, d), 7.56 (2H, d),7.90 (4H, d), 9.67 (2H, —OH) ppm.

¹³C-NMR (150 MHz in DMSO-d₆): δ=25.45, 61.98, 66.96, 108.30, 114.19,118.69, 120.45, 125.05, 125.96, 126.19, 126.85, 127.12, 127.49, 127.73,128.72, 129.28, 133.29, 137.25, 139.44, 139.66, 151.00, 155.30, 157.32ppm.

TG-DTA (−5% weight loss temperature, in Air):395° C.

TG-DTA (−5% weight loss temperature, in He):368° C.

DSC (Glass transition temperature): 138° C.

Synthetic Example 7 Synthesis of Compound (IV)

Under nitrogen atmosphere, in a 3 L four necked flask equipped with athermometer and a reflux condenser were charged 50.0 g (289.0 mmol) of4-bromophenol, 3.3 g (14.5 mmol) of benzyltriethylammonium chloride,55.5 g of 25% aqueous sodium hydroxide solution and 170 ml oftetrahydrofuran, and the mixture was heated in an oil bath at 60° C. Tothe mixture was added dropwise 31.7 g (129.9 mmol) of 1,6-dibromohexanepreviously diluted with 35 g of tetrahydrofuran from a dropping funnelover 20 minutes, and the mixture was stirred under reflux for 50 hours.After diluting the mixture with 200 ml of toluene, the mixture wascooled to room temperature by allowing to stand, and transferred to aseparating funnel. The aqueous layer was disposed, the organic layer wasfurther washed twice with 100 g of 5% aqueous sodium hydroxide solution,and separation of the liquids and washing with water were repeated untilthe aqueous layer became neutral. The organic layer was recovered anddried over anhydrous sodium sulfate, then, the drier was removed byfiltration and the solvent of the filtrate was removed by using anevaporator. The obtained crystal is vacuum dried at 45° C. to obtain54.0 g of Compound (IV) with a yield of 97.1% and a GPC purity of 98.2%.

Compound (IV):

IR (ATR method): ν=3091, 2942, 2910, 2864, 1885, 1637, 1589, 1576, 1490,1474, 1398, 1290, 1248, 1175, 1119, 1105, 1076, 1025, 1001, 830, 809,733 cm⁻¹.

¹H-NMR (600 MHz in CDCL3): δ=1.53 (4H, quint), 1.80 (4H, quint), 3.93(4H, t), 6.77 (4H, d-t), 7.36 (4H, d-t) ppm.

¹³C-NMR (150 MHz in CDCl₃): δ=25.78, 29.07, 68.02, 112.61, 116.25,132.18, 158.15 ppm.

Synthetic Example 8 Synthesis of Compound (V)

Under nitrogen atmosphere, in a 2000 ml four necked flask equipped witha thermometer and a reflux condenser was weighed 40.0 g (93.4 mmol) ofCompound (IV), 300 ml of tetrahydrofuran was added thereto to prepare auniform solution. The flask was cooled with acetonitrile-dry icerefrigerant, and to the mixture was added dropwise 79.1 ml of 2.6 mol/Ln-butyl lithium-hexane solution from a dropping funnel over 20 minutes,and the mixture was stirred for 1 hour. Then, the refrigerant waschanged to an ice-cooling bath and 202.0 g of 15 wt %9-fluorenone-tetrahydrofuran solution was added dropwise to the mixturefrom a dropping funnel over 15 minutes. After stirring at roomtemperature for 19 hours, the reaction was stopped by adding 200 ml of asaturated aqueous ammonium chloride solution to the mixture. Thereaction mixture was diluted with 600 ml of ethyl acetate, transferredto a separating funnel and separation of liquids and washing with waterwere repeated until the aqueous layer became neutral. The organic layerwas recovered, and after removing the solvent by distillation until theinner composition in an evaporator became 196 g, and 589 g of hexane wasadded to the mixture under stirring to precipitate a rice cake-likelump. The supernatant was removed by decantation and 50 g of ethylacetate was added again to the residue to prepare a uniform solution,and 472 g of hexane was added to the mixture under stirring toprecipitate a rice cake-like lump again. The supernatant was removed bydecantation and the precipitate was recrystallized from 215 g of ethylacetate/isopropyl alcohol=1/6 (weight ratio). The crystals werecollected by filtration using a Hirsch funnel, and washed twice with 100g of isopropyl alcohol and vacuum dried at 60° C. to obtain 11.7 g ofCompound (V) with a yield of 22.1% and a GPC purity of 97.4%.

Compound (V):

IR (ATR method): ν=3529, 3443, 3038, 2935, 2868, 1608, 1582, 1471, 1448,1415, 1385, 1295, 1248, 1166, 1115, 1099, 1031, 1010, 995, 946, 919,827, 770, 750, 734 cm⁻¹.

¹H-NMR (600 MHz in DMSO-d₆): δ=1.39 (4H, m), 1.64 (4H, m), 3.86 (4H, t),6.18 (2H, —OH), 6.76 (4H, d-t), 7.11 (4H, d-t), 7.21 to 7.25 (8H, m),7.34 (4H, m), 7.77 (4H, d) ppm.

¹³C-NMR (150 MHz in DMSO-d₆): δ=25.23, 28.59, 67.19, 82.22, 113.82,119.99, 124.57, 126.24, 127.93, 128.32, 136.80, 139.01, 151.48, 157.48ppm.

Synthetic Example 9 Synthesis of Compound (A4)

Under nitrogen atmosphere, in 200 ml of three necked flask equipped witha thermometer and a reflux condenser were weighed 5.0 g (7.9 mmol) ofCompound (V) and 6.0 g (63.8 mmol) of phenol, 50 ml of methylenechloride was added to the mixture to prepare a uniform solution in anoil bath at 30° C. To the mixture was gradually added dropwise 2.5 ml ofmethanesulfonic acid from a dropping funnel, and the mixture was heatedfor 40 minutes. After cooling the mixture to room temperature byallowing to stand, the mixture was diluted with 150 ml of methylisobutyl ketone, transferred to a separating funnel, and separation ofthe liquids and washing with water were repeated until the aqueous layerbecame neutral. The organic layer was recovered, and after removing thesolvent by distillation until the inner composition in an evaporatorbecame 22 g, 88 g of hexane was added dropwise under stirring toprecipitate a rice cake-like lump. The supernatant was removed bydecantation, 12 g of ethyl acetate and 88 g of methanol were added tothe lump to carry out recrystallization. The crystals were collected byfiltration using a Hirsch funnel, washed twice with 50 g of methanol andvacuum dried at 60° C. to obtain 2.9 g of Compound (A4) with a yield of46.7% and a GPC purity of 93.8%.

Compound (A4):

IR (ATR method): ν=3540, 3414, 3062, 2940, 2866, 1609, 1506, 1474, 1447,1394, 1330, 1292, 1266, 1238, 1181, 1171, 1118, 1105, 1017, 917, 823,803, 746, 731 cm⁻¹.

¹H-NMR (600 MHz in DMSO-d₆): δ=1.38 (4H, m), 1.64 (4H, m), 3.85 (4H, t),6.61 (4H, d-t), 6.75 (4H, d-t), 6.89 (4H, d-t), 6.96 (4H, d-t), 7.27(4H, t-d), 7.32 to 7.36 (8H, m), 7.87 (4H, m), 9.30 (2H, —OH) ppm.

¹³C-NMR (150 MHz in DMSO-d₆): δ=25.22, 28.58, 63.56, 67.19, 114.03,114.93, 120.35, 125.86, 127.32, 127.65, 128.61, 128.64, 135.69, 137.61,139.30, 151.45, 156.02, 157.27 ppm.

TG-DTA (−5% weight loss temperature, in Air): 350° C.

TG-DTA (−5% weight loss temperature, in He): 356° C.

DSC (Glass transition temperature): 109° C.

Synthetic Example 10 Synthesis of Compound (A5)

Under nitrogen atmosphere, in 200 ml of three necked flask equipped witha thermometer and a reflux condenser were weighed 5.0 g (7.9 mmol) ofCompound (V) and 9.1 g (63.1 mmol) of 2-naphthol, and 100 ml ofmethylene chloride was added to the mixture to prepare a uniformsolution in an oil bath at 30° C. To the mixture was gradually addeddropwise 2.5 ml of methanesulfonic acid from a dropping funnel, and themixture was heated for 2 hours. After cooling the mixture to roomtemperature by allowing to stand, the mixture was diluted with 220 ml ofmethyl isobutyl ketone, transferred to a separating funnel, andseparation of the liquids and washing with water were repeated until theaqueous layer became neutral. The organic layer was recovered, and afterremoving the solvent by distillation until the inner composition in anevaporator became 17 g, 25 g of ethyl acetate and 113 g of isopropylalcohol were added to the residue to carry out recrystallization. Thecrystals were collected by filtration using a Hirsch funnel, washedtwice with 50 g of isopropyl alcohol and vacuum dried at 60° C. toobtain 4.0 g of Compound (A5) with a yield of 57.1% and a GPC purity of95.0%.

Compound (A5):

IR (ATR method): ν=3545, 3361, 3062, 2941, 2874, 1634, 1605, 1580, 1505,1475, 1447, 1390, 1348, 1278, 1250, 1223, 1204, 1180, 1147, 1122, 1021,959, 923, 898, 884, 862, 839, 823, 807, 751, 737 cm⁻¹.

¹H-NMR (600 MHz in DMSO-d₆): δ=1.40 (4H, m), 1.65 (4H, m), 3.87 (4H, t),6.79 (4H, d), 6.97 (4H, d-d), 7.00 to 7.04 (6H, m), 7.18 (2H, d-d), 7.29(4H, t), 7.34 to 7.39 (6H, m), 7.44 (4H, d), 7.51 (2H, d), 7.56 (2H, d),7.91 (4H, d), 9.67 (2H, —OH) ppm.

¹³C-NMR (150 MHz in DMSO-d₆): δ=25.22, 28.58, 64.14, 67.20, 108.30,114.15, 118.70, 120.48, 125.05, 125.98, 126.21, 126.87, 127.12, 127.52,127.76, 128.73, 129.30, 133.29, 137.19, 139.45, 139.68, 151.01, 155.30,157.39 ppm.

TG-DTA (−5% weight loss temperature, in Air): 388° C.

TG-DTA (−5% weight loss temperature, in He): 398° C.

DSC (Glass transition temperature): 132° C.

Synthetic Example 11 Synthesis of Compound (A6)

Under nitrogen atmosphere, in 200 ml of three necked flask equipped witha thermometer and a reflux condenser were weighed 10.0 g (13.2 mmol) ofCompound (A2), 0.30 g (1.3 mmol) of benzyltriethylammonium chloride, 4.7g of 25% aqueous sodium hydroxide solution and 50 ml of tetrahydrofuran,and the mixture was heated in an oil bath at 60° C. To the mixture wasadded dropwise 0.95 g (4.4 mmol) of 1,4-dibromobutane previously dilutedwith 5 g of tetrahydrofuran from a dropping funnel over 5 minutes, andthe mixture was heated under reflux for 21 hours. After diluting themixture with 40 ml of methyl isobutyl ketone, 20% hydrochloric acid wasadded to the mixture in an ice-bath until the solution became acidic.The mixture was transferred to a separating funnel, and separation ofthe liquids and washing with water were repeated until the aqueous layerbecame neutral. The organic layer was recovered and the solvent wasremoved by evaporation. To the polymer evaporated to dryness was addedtetrahydrofuran, and 37 g of a polymer solution thus prepared was addeddropwise to 164 g of isopropyl alcohol to precipitate a polymer. Theprecipitated polymer was collected by filtration, further washed twicewith 60 g of isopropyl alcohol and vacuum dried at 60° C. to obtain 5.9g of Compound (A6) with a yield of 57.6%.

Compound (A6):

GPC (RI): Mw=2070, Mn=1390, Mw/Mn=1.49

n=to 1.8 (calculated from Mn), to 2.0 (calculated from ¹H-NMR).

IR (ATR method): ν=3546, 3035, 2944, 1607, 1506, 1472, 1447, 1390, 1292,1243, 1176, 1115, 1013, 915, 823, 745, 729 cm⁻¹.

TG-DTA (−5% weight loss temperature, in Air): 361° C.

TG-DTA (−5% weight loss temperature, in He): 366° C.

DSC (Glass transition temperature): 136° C.

Synthetic Example 12 Synthesis of Compound (A7)

Under nitrogen atmosphere, in 200 ml of three necked flask equipped witha thermometer and a reflux condenser were weighed 20.0 g (57.1 mmol) of9,9-bis(4-hydroxyphenyl)-fluorene, 0.65 g (2.9 mmol) ofbenzyltriethylammonium chloride, 20.1 g of 25% aqueous sodium hydroxidesolution and 50 ml of tetrahydrofuran, and the mixture was heated in anoil bath at 60° C. To the mixture was added dropwise 4.11 g (19.0 mmol)of 1,4-dibromobutane previously diluted with 5 g of tetrahydrofuran froma dropping funnel over 10 minutes, and the mixture was heated underreflux for 28 hours. To the mixture were added 50 ml of methyl isobutylketone and 100 ml of tetrahydrofuran, 20% hydrochloric acid was added tothe mixture in an ice-bath until the solution became acidic. The mixturewas transferred to a separating funnel, and separation of the liquidsand washing with water were repeated until the aqueous layer becameneutral. The organic layer was recovered and the solvent was removed bydistillation. To the polymer evaporated to dryness was addedtetrahydrofuran, 70 g of a polymer solution thus prepared was addeddropwise to 420 g of methanol to precipitate a polymer. The precipitatedpolymer was collected by filtration, further washed twice with 100 g ofmethanol and vacuum dried at 60° C. to obtain 4.9 g of Compound (A7)with a yield of 23.3%.

Compound (A7):

GPC (RI): Mw=2510, Mn=1490, Mw/Mn=1.68

n=to 3.8 (calculated from Mn), to 4.0 (calculated from ¹H-NMR).

IR (ATR method): ν=3526, 3034, 2948, 1606, 1505, 1427, 1446, 1388, 1290,1242, 1175, 1113, 1013, 915, 822, 744, 729 cm⁻¹.

TG-DTA (−5% weight loss temperature, in Air): 363° C.

TG-DTA (−5% weight loss temperature, in He): 368° C.

DSC (Glass transition temperature): 139° C.

Synthetic Example 13 Synthesis of Compound (A8)

Under nitrogen atmosphere, in 200 ml of three necked flask equipped witha thermometer and a reflux condenser were weighed 10.0 g (13.3 mmol) ofCompound (A2) and 0.75 g (corresponding to 9.3 mmol of formalin) of 37%aqueous formalin solution, 40 ml of propylene glycol monomethyl etherwas added to the mixture to prepare a uniform solution in an oil bath at90° C. To the mixture was gradually added dropwise 2.5 g of a propyleneglycol monomethyl ether solution containing 20 wt % of p-toluenesulfonicacid monohydrate previously prepared from a dropping funnel. Aftercompletion of the dropwise addition, the reaction was carried out in anoil bath at 120° C. for 19 hours. The mixture was cooled at roomtemperature by allowing to stand, diluted with 200 ml of methyl isobutylketone, transferred to a separating funnel and separation of liquids andwashing with water were repeated until the aqueous layer became neutral.The organic layer was recovered and the solvent was removed bydistillation using an evaporator. The residue was recovered and vacuumdried at 60° C. to obtain 8.8 g of Compound (A8) with a yield of 87.0%.

Compound (A8):

GPC (RI): Mw=3880, Mn=1570, Mw/Mn=2.47

Synthetic Example 14 Synthesis of Compound (A9)

Under nitrogen atmosphere, in 100 ml of three necked flask equipped witha thermometer and a reflux condenser were weighed 4.71 g (7.8 mmol) ofCompound (III) and 1.69 g (11.7 mmol) of 2-naphthol, and 25 ml of1,2-dichloroethane was added to the mixture to prepare a uniformsolution in an oil bath at 60° C. To the mixture was gradually addeddropwise 0.5 ml of methanesulfonic acid from a dropping funnel, and thereaction was carried out in an oil bath at 60° C. for 8 hours. Themixture was cooled at room temperature by allowing to stand, dilutedwith 100 ml of methyl isobutyl ketone, transferred to a separatingfunnel, and separation of the liquids and washing with water wererepeated until the aqueous layer became neutral. The organic layer wasrecovered, and after removing the solvent by distillation until theinner composition in an evaporator became 20.6 g, the reside was addeddropwise to 122 g of methanol:water=4:1 (weight ratio) to precipitate apolymer. The precipitated polymer was collected by filtration using aHirsch funnel, washed twice with 36 g of methanol:water=4:1 (weightratio) and vacuum dried at 60° C. to obtain 5.8 g of Compound (A9) witha yield of 94.7%.

Compound (A9):

GPC (RI): Mw=2320, Mn=1350, Mw/Mn=1.72

Synthetic Example 15 Synthesis of Compound (A10)

Under nitrogen atmosphere, in 100 ml of three necked flask equipped witha thermometer and a reflux condenser were weighed 7.28 g (12.1 mmol) ofCompound (III) and 2.90 g (18.1 mmol) of 1,7-dihydroxynaphthalene, and50 ml of 1,2-dichloroethane was added to the mixture to prepare asuspended solution in an oil bath at 50° C. To the suspension wasgradually added dropwise 0.24 ml of methanesulfonic acid from a droppingfunnel, and the reaction was carried out in an oil bath at 60° C. for1.5 hours. The mixture was cooled at room temperature by allowing tostand, diluted with 100 ml of methyl isobutyl ketone, transferred to aseparating funnel, and separation of the liquids and washing with waterwere carried out until the aqueous layer became neutral. The organiclayer was recovered and the solvent was removed by distillation. To theresidue was added tetrahydrofuran, and 40 g of the polymer solution thusprepared was added dropwise to 150 g of methanol:water=4:1 (weightratio) to precipitate a polymer. The precipitated polymer was collectedby filtration using a Hirsch funnel, washed twice with 50 g ofmethanol:water=4:1 (weight ratio) and vacuum dried at 60° C. to obtain8.2 g of Compound (A10) with a yield of 84.2%.

Compound (A10):

GPC (RI): Mw=3410, Mn=1880, Mw/Mn=1.81

Synthetic Example 16 Synthesis of Compound (A11)

Under nitrogen atmosphere, in 100 ml of three necked flask equipped witha thermometer and a reflux condenser were weighed 8.9 g (14.8 mmol) ofCompound (III) and 8.9 g (19.8 mmol) of6,6-(9-fluorenylidene)-di(2-naphthol), and 60 ml of γ-butyrolactone wasadded to the mixture to prepare a uniform solution in an oil bath at 60°C. To the mixture was gradually added dropwise 4.8 ml of methanesulfonicacid from a dropping funnel, and the reaction was carried out in an oilbath at 60° C. for 1.5 hours. The mixture was cooled at room temperatureby allowing to stand, diluted with 120 ml of methyl isobutyl ketone,transferred to a separating funnel, and separation of the liquids andwashing with water were repeated until the aqueous layer became neutral.The organic layer was recovered and the solvent was removed bydistillation. To the residue was added tetrahydrofuran, and 63 g of apolymer solution thus prepared was added dropwise to 150 g of methanolto precipitate a polymer. The precipitated polymer was collected byfiltration using a Hirsch funnel, washed twice with 80 g of methanol andvacuum dried at 60° C. to obtain 9.9 g of Compound (A11) with a yield of57.2%.

Compound (A10):

GPC (RI): Mw=4040, Mn=2580, Mw/Mn=1.57

Synthetic Example 17 Synthesis of Compound (VI)

Under nitrogen atmosphere, in 300 ml of three necked flask equipped witha thermometer and a reflux condenser were weighed 25.0 g (201.4 mmol) of4-hydroxybenzyl alcohol, 18.5 g (85.6 mmol) of 1,4-dibromobutane and30.6 g (221.5 mmol) of potassium carbonate, 50 g of dimethylformamidewas added to the mixture and the reaction was carried out in an oil bathat 40° C. for 24 hours. The mixture was cooled at room temperature byallowing to stand, diluted with 130 ml of water, 300 ml oftetrahydrofuran and 60 ml of toluene, and transferred to a separatingfunnel. The aqueous layer was removed and washed with 60 g of 5 wt %aqueous sodium hydroxide solution, and separation of the liquids andwashing with water were repeated until the aqueous layer became neutral.The solvent was removed by distillation until the inner composition inan evaporator became 130 g, and 156 g of diisopropyl ether was addeddropwise to the residue under stirring to precipitate crystals. Thecrystals were collected by filtration using a Hirsch funnel, washedtwice with 50 g of diisopropyl ether and vacuum dried at 50° C. toobtain 19.4 g of Compound (VI) with a yield of 74.9% and a GPC purity of94.9%.

Compound (VI):

IR (ATR method): ν=3332, 2955, 2929, 2908, 2870, 1612, 1586, 1512, 1474,1448, 1386, 1303, 1249, 1212, 1198, 1174, 1167, 1110, 1052, 1039, 1009,997, 977, 929, 827, 808, 790 cm⁻¹.

¹H-NMR (600 MHz in DMSO-d₆): δ=1.84 (4H, m), 3.99 (4H, t), 4.39 (4H, d),5.02 (—OH, t), 6.87 (4H, d-t), 7.20 (4H, d-t) ppm.

¹³C-NMR (150 MHz in DMSO-d₆): δ=26.00, 63.12, 67.63, 114.57, 128.45,135.01, 158.04 ppm.

Synthetic Example 18 Synthesis of Compound (A12)

Under nitrogen atmosphere, in 100 ml of three necked flask equipped witha thermometer and a reflux condenser were weighed 3.15 g (10.4 mmol) ofCompound (VI) and 2.0 g (13.9 mmol) of 2-naphthol, and 20 ml ofγ-butyrolactone was added to the mixture to prepare a uniform solutionin an oil bath at 80° C. To the mixture was gradually added dropwise 1.0g of a γ-butyrolactone solution containing 20 wt % of p-toluenesulfonicacid monohydrate previously prepared from a dropping funnel. Aftercompletion of the dropwise addition, the reaction was carried out in anoil bath at 80° C. for 3 hours. The mixture was cooled at roomtemperature by allowing to stand, diluted with 100 ml of methyl isobutylketone, transferred to a separating funnel, and separation of liquidsand washing with water were repeated until the aqueous layer becameneutral. The organic layer was recovered, and the solvent was removed bydistillation by an evaporator. The residue was recovered and vacuumdried at 60° C. to obtain 4.6 g of Compound (A2) with a yield of 96.4%.

Compound (A12):

GPC (RI): Mw=1720, Mn=880, Mw/Mn=1.95

Synthetic Example 19 Synthesis of Compound (A13)

Under nitrogen atmosphere, in 100 ml of three necked flask equipped witha thermometer and a reflux condenser were weighed 4.25 g (14.0 mmol) ofCompound (VI) and 3.0 g (18.7 mmol) of 1,5-dihydroxynaphthalene, and 30ml of γ-butyrolactone was added to the mixture to prepare a uniformsolution in an oil bath at 80° C. To the mixture was gradually addeddropwise 1.0 g of a γ-butyrolactone solution containing 20 wt % ofp-toluenesulfonic acid monohydrate previously prepared from a droppingfunnel. After completion of the dropwise addition, the reaction wascarried out in an oil bath at 80° C. for 3 hours. After cooling themixture to room temperature by allowing to stand, the mixture wasdiluted with 100 ml of methyl isobutyl ketone, transferred to aseparating funnel, and separation of liquids and washing with water wererepeated until the aqueous layer became neutral. The organic layer wasrecovered, and the solvent was removed by distillation by an evaporator.The residue was recovered and vacuum dried at 60° C. to obtain 5.9 g ofCompound (A13) with a yield of 87.5%.

Compound (A13):

GPC (RI): Mw=6960, Mn=1250, Mw/Mn=5.57

Synthetic Example 20 Synthesis of Compound (A14)

Under nitrogen atmosphere, in 200 ml of three necked flask equipped witha thermometer and a reflux condenser were weighed 5.61 g (18.6 mmol) ofCompound (VI) and 10.0 g (28.5 mmol) of9,9-bis(4-hydroxyphenyl)fluorene, and 40 ml of propylene glycolmonomethyl ether was added to the mixture to prepare a uniform solutionin an oil bath at 90° C. To the mixture was gradually added dropwise 2.5g of a propylene glycol monomethyl ether solution containing 20 wt % ofp-toluenesulfonic acid monohydrate previously prepared from a droppingfunnel. After completion of the dropwise addition, the reaction wascarried out in an oil bath at 120° C. for 5 hours. After cooling themixture to room temperature by allowing to stand, the mixture wasdiluted with 200 ml of methyl isobutyl ketone, transferred to aseparating funnel, and separation of liquids and washing with water wererepeated until the aqueous layer became neutral. The organic layer wasrecovered, and the solvent was removed by distillation by an evaporator.The residue was recovered and vacuum dried at 60° C. to obtain 13.5 g ofCompound (A14) with a yield of 90.4%.

Compound (A14):

GPC (RI): Mw=20530, Mn=1160, Mw/Mn=17.70

Synthetic Example 21 Synthesis of Compound (A15)

Under nitrogen atmosphere, in 200 ml of three necked flask equipped witha thermometer and a reflux condenser were weighed 2.80 g (9.27 mmol) ofCompound (VI) and 10.0 g (13.3 mmol) of Compound (A2), and 40 ml ofγ-butyrolactone was added to the mixture to prepare a uniform solutionin an oil bath at 90° C. To the mixture was gradually added dropwise 2.5g of a γ-butyrolactone solution containing 20 wt % of p-toluenesulfonicacid monohydrate previously prepared from a dropping funnel. Aftercompletion of the dropwise addition, the reaction was carried out in anoil bath at 120° C. for 3 hours. After cooling the mixture to roomtemperature by allowing to stand, the mixture was diluted with 200 ml ofmethyl isobutyl ketone, transferred to a separating funnel, andseparation of liquids and washing with water were repeated until theaqueous layer became neutral. The organic layer was recovered, and thesolvent was removed by distillation by an evaporator. The residue wasrecovered and vacuum dried at 60° C. to obtain 11.4 g of Compound (A15)with a yield of 91.4%.

Compound (A15):

GPC (RI): Mw=18110, Mn=1840, Mw/Mn=9.84

Synthetic Example 22 Synthesis of Compound (A16)

Under nitrogen atmosphere, in 200 ml of three necked flask equipped witha thermometer and a reflux condenser were weighed 4.36 g (14.4 mmol) ofCompound (VI) and 10.0 g (22.2 mmol) of6,6-(9-fluorenylidene)-di(2-naphthol), and 40 ml of propylene glycolmonomethyl ether was added to the mixture to prepare a uniform solutionin an oil bath at 90° C. To the mixture was gradually added dropwise 2.5g of a propylene glycol monomethyl ether solution containing 20 wt % ofp-toluenesulfonic acid monohydrate previously prepared from a droppingfunnel. After completion of the dropwise addition, the reaction wascarried out in an oil bath at 120° C. for 5 hours. After cooling themixture to room temperature by allowing to stand, the mixture wasdiluted with 200 ml of methyl isobutyl ketone, transferred to aseparating funnel, and separation of liquids and washing with water wererepeated until the aqueous layer became neutral. The organic layer wasrecovered, and the solvent was removed by distillation by an evaporator.The residue was recovered and vacuum dried at 60° C. to obtain 12.4 g ofCompound (A16) with a yield of 89.6%.

Compound (A16):

GPC (RI): Mw=3580, Mn=1350, Mw/Mn=2.64

Synthetic Example 23 Synthesis of Compound (VII)

Reaction and purification were carried out in the same manner as inSynthetic example 17 except for using 25.0 g of 2-hydroxybenzyl alcoholin place of 25.0 g of 4-hydroxybenzyl alcohol. As a result, 23.5 g ofthe objective compound, Compound (VII) was obtained with a yield of80.6% and a GPC purity of 79.0%.

Compound (VII):

IR (ATR method): ν=3206, 2959, 2914, 2873, 1601, 1590, 1493, 1472, 1455,1396, 1375, 1305, 1282, 1156, 1111, 1060, 1039, 1016, 945, 926, 850,838, 749 cm⁻¹.

¹H-NMR (600 MHz in DMSO-d₆): δ=1.88 (4H, m), 4.02 (4H, t), 4.52 (4H, d),4.95 (—OH, t), 6.90 to 6.95 (4H, m), 7.18 (2H, t-d), 7.38 (2H, d) ppm.

¹³C-NMR (150 MHz in DMSO-d₆): δ=25.75, 57.98, 67.29, 111.11, 120.18,127.02, 127.66, 130.68, 155.44 ppm.

Synthetic Example 24 Synthesis of Compound (A17)

Under nitrogen atmosphere, in 200 ml of three necked flask equipped witha thermometer and a reflux condenser were weighed 4.36 g (14.4 mmol) ofCompound (VII) and 10.0 g (22.2 mmol) of6,6-(9-fluorenylidene)-di(2-naphthol), and 40 ml of γ-butyrolactone wasadded to the mixture to prepare a uniform solution in an oil bath at 90°C. To the mixture was gradually added dropwise 2.5 g of aγ-butyrolactone solution containing 20 wt % of p-toluenesulfonic acidmonohydrate previously prepared from a dropping funnel. After completionof the dropwise addition, the reaction was carried out in an oil bath at120° C. for 3 hours. After cooling the mixture to room temperature byallowing to stand, the mixture was diluted with 200 ml of methylisobutyl ketone, transferred to a separating funnel, and separation ofliquids and washing with water were repeated until the aqueous layerbecame neutral. The organic layer was recovered and the solvent wasremoved by distillation. To the reside was added tetrahydrofuran, and 40g of a polymer solution thus prepared was added dropwise to 200 g ofmethanol to precipitate a polymer. The precipitated polymer wascollected by filtration using a Hirsch funnel, washed twice with 80 g ofmethanol and vacuum dried at 60° C. to obtain 6.7 g of Compound (A17)with a yield of 48.4%.

Compound (A17):

GPC (RI): Mw=3800, Mn=2190, Mw/Mn=1.74

Synthetic Example 25 Synthesis of Compound (VIII)

Reaction and purification were carried out in the same manner as inSynthetic example 17 except for using 25.68 g of 1,10-dibromodecane inplace of 18.5 g of 1,4-dibromobutane. As a result, 23.3 g of theobjective compound, Compound (VIII) was obtained with a yield of 70.4%and a GPC purity of 94.5%.

Compound (VIII):

IR (ATR method): ν=3327, 2936, 2921, 2852, 1611, 1582, 1512, 1475, 1464,1395, 1300, 1171, 1113, 1049, 1016, 836, 820, 800 cm⁻¹.

¹H-NMR (600 MHz in DMSO-d₆): δ=1.24 to 1.36 (8H, m), 1.38 (4H, quint),1.67 (4H, quint), 3.90 (4H, t), 4.39 (4H, d), 5.01 (—OH, t), 6.84 (4H,d-t), 7.18 (4H, d) ppm.

Synthetic Example 26 Synthesis of Compound (A18)

Under nitrogen atmosphere, in 100 ml of three necked flask equipped witha thermometer and a reflux condenser were weighed 5.27 g (13.6 mmol) ofCompound (VIII) and 2.0 g (18.2 mmol) of resorcinol, and 30 ml ofpropylene glycol monomethyl ether was added to the mixture to prepare auniform solution in an oil bath at 90° C. To the mixture was graduallyadded dropwise 1.0 g of a propylene glycol monomethyl ether solutioncontaining 20 wt % of p-toluenesulfonic acid monohydrate previouslyprepared from a dropping funnel. After completion of the dropwiseaddition, the reaction was carried out in an oil bath at 120° C. for 4hours. After cooling the mixture to room temperature by allowing tostand, the mixture was diluted with 200 ml of methyl isobutyl ketone,transferred to a separating funnel, and separation of liquids andwashing with water were repeated until the aqueous layer became neutral.The organic layer was recovered, the solvent was removed by distillationby an evaporator, and the residue was recovered and vacuum dried at 60°C. to obtain 5.8 g of Compound (A18) with a yield of 85.6%.

Compound (A18):

GPC (RI): Mw=6020, Mn=1230, Mw/Mn=4.89

Synthetic Example 27 Synthesis of Compound (A19)

Under nitrogen atmosphere, in 200 ml of three necked flask equipped witha thermometer and a reflux condenser were weighed 9.19 g (23.8 mmol) ofCompound (VIII) and 10.0 g (26.4 mmol) of9,9-bis(4-hydroxy-3-methylphenyl)fluorine, and 50 ml of propylene glycolmonopropyl ether was added to the mixture in an oil bath at 90° C. toprepare a uniform solution. To the mixture was gradually added dropwise2.5 g of a propylene glycol monopropyl ether solution containing 20 wt %of p-toluenesulfonic acid monohydrate previously prepared from adropping funnel. After completion of the dropwise addition, the reactionwas carried out in an oil bath at 150° C. for 8 hours. After cooling themixture to room temperature by allowing to stand, and the mixture wasdiluted with 200 ml of methyl isobutyl ketone, transferred to aseparating funnel, and separation of liquids and washing with water wererepeated until the aqueous layer became neutral. The organic layer wasrecovered, and the solvent was removed by distillation by an evaporator.The residue was recovered and vacuum dried at 60° C. to obtain 17.5 g ofCompound (A19) with a yield of 95.4%.

Compound (A19):

GPC (RI): Mw=13250, Mn=2410, Mw/Mn=5.50

Synthetic Example 28 Synthesis of Compound (A20)

Under nitrogen atmosphere, in 200 ml of three necked flask equipped witha thermometer and a reflux condenser were weighed 6.86 g (17.8 mmol) ofCompound (VIII) and 10.0 g (22.2 mmol) of6,6-(9-fluorenylidene)-di(2-naphthol), and 50 ml of propylene glycolmonomethyl ether was added to the mixture to prepare a uniform solutionin an oil bath at 90° C. To the mixture was gradually added dropwise 2.5g of a propylene glycol monomethyl ether solution containing 20 wt % ofp-toluenesulfonic acid monohydrate previously prepared from a droppingfunnel. After completion of the dropwise addition, the reaction wascarried out in an oil bath at 120° C. for 4 hours. After cooling themixture to room temperature by allowing to stand, the mixture wasdiluted with 200 ml of methyl isobutyl ketone, transferred to aseparating funnel, and separation of liquids and washing with water wererepeated until the aqueous layer became neutral. The organic layer wasrecovered, and the solvent was removed by distillation by an evaporator.The residue was recovered and vacuum dried at 60° C. to obtain 14.9 g ofCompound (A20) with a yield of 91.8%.

Compound (A20):

GPC (RI): Mw=8760, Mn=2460, Mw/Mn=3.56

(Comparison Polymer) Liquid State Additive (B1)

Preparation of Resist Underlayer Film Compositions (UDL-1 to 23,Comparative UDL-1 to 5)

The Compounds (A1) to (A20), a liquid state additive (B1), base resinscontaining an aromatic ring represented by (R1) to (R3), cross-linkingagents represented by CR1 and CR2, an acid generator represented by AG1and a solvent were dissolved in a medium containing 0.1% by mass ofFC-4430 (product of Sumitomo 3M Limited) with ratios shown in Table 1,and filtered through a 0.1 μm filter made of a fluorine resin to prepareresist underlayer film compositions (ULD-1 to 23, Comparative UDL-1 to5), respectively.

TABLE 1 Compound Base resin Cross-linking agent Acid generator SolventComposition (parts by mass) (parts by mass) (parts by mass) (parts bymass) (parts by mass) UDL-1  A2 (10) None CR1 (2) AG1 (1) PGMEA (90)UDL-2  A6 (10) None PGMEA (63)/ cyclohexanone (27) UDL-3  A7 (10) NonePGMEA (63)/ cyclohexanone (27) UDL-4 A1 (5) R1 (5) PGMEA (63)/cyclohexanone (27) UDL-5 A2 (5) R1 (5) PGMEA (63)/ cyclohexanone (27)UDL-6 A3 (5) R1 (5) PGMEA (63)/ cyclohexanone (27) UDL-7 A4 (5) R1 (5)PGMEA (63)/ cyclohexanone (27) UDL-8 A5 (5) R1 (5) PGMEA (63)/cyclohexanone (27) UDL-9 A2 (5) R2 (5) PGMEA (90) UDL-10 A2 (5) R3 (5)CR2 (2) AG1 (1) PGMEA (90) UDL-11  A8 (10) None PGMEA (90) UDL-12  A9(10) None PGMEA (90) UDL-13 A10 (10) None PGMEA (90) UDL-14 A11 (10)None PGMEA (90) UDL-15 A12 (10) None PGMEA (90) UDL-16 A13 (10) NonePGMEA (90) UDL-17 A14 (10) None PGMEA (90) UDL-18 A15 (10) None PGMEA(90) UDL-19 A16 (10) None PGMEA (90) UDL-20 A17 (10) None PGMEA (90)UDL-21 A18 (10) None PGMEA (90) UDL-22 A19 (10) None PGMEA (90) UDL-23A20 (10) None PGMEA (90) Comparative None  R1 (10) PGMEA (63)/ UDL-1cyclohexanone (27) Comparative None  R2 (10) PGMEA (90) UDL-2Comparative None  R3 (10) CR2 (2) AG1 (1) PGMEA (90) UDL-3 ComparativeB1 (5) R1 (5) PGMEA (63)/ UDL-4 cyclohexanone (27) Comparative B1 (2) R1 (10) PGMEA (63)/ UDL-5 cyclohexanone (27) PGMEA: Propylene glycolmonomethyl ether acetate

(R1) to (R3) used as the base resins containing an aromatic ring, CR1and CR2 used as the cross-linking agents, and AG1 used as an acidgenerator are shown below.

Measurement of Solvent Resistance Examples 1-1 to 1-23, ComparativeExamples 1-1 to 1-5

The prepared resist underlayer film compositions (UDL-1 to 23,Comparative UDL-1 to 5) were coated on a silicon substrate, baked underthe conditions shown in Table 2, and then, the film thickness wasmeasured, respectively. The film thickness was measured, and a PGMEAsolvent was dispensed thereon, allowed to stand for 30 seconds and spindried, and baked at 100° C. for 60 seconds to evaporate the PGMEA. Then,the film thickness was measured again to obtain a difference in the filmthickness before and after the PGMEA treatment.

TABLE 2 Film Film thickness thickness after film after PGMEA Bakingformation: treatment: b/a × temperature Composition a (Å) b (Å) 100 (%)(° C.) Example 1-1 UDL-1 2845 2843 100 350° C. × 60 sec Example 1-2UDL-2 2830 2829 100 350° C. × 60 sec Example 1-3 UDL-3 2821 2820 100350° C. × 60 sec Example 1-4 UDL-4 2876 2875 100 350° C. × 60 secExample 1-5 UDL-5 2769 2769 100 350° C. × 60 sec Example 1-6 UDL-6 28122810 100 350° C. × 60 sec Example 1-7 UDL-7 2809 2809 100 350° C. × 60sec Example 1-8 UDL-8 2853 2852 100 350° C. × 60 sec Example 1-9 UDL-92795 2794 100 350° C. × 60 sec Example 1-10 UDL-10 2820 2818 100 250° C.× 60 sec Example 1-11 UDL-11 2968 2967 100 350° C. × 60 sec Example 1-12UDL-12 2860 2858 100 350° C. × 60 sec Example 1-13 UDL-13 2912 2911 100350° C. × 60 sec Example 1-14 UDL-14 2926 2925 100 350° C. × 60 secExample 1-15 UDL-15 2893 2892 100 350° C. × 60 sec Example 1-16 UDL-162956 2955 100 350° C. × 60 sec Example 1-17 UDL-17 2914 2913 100 350° C.× 60 sec Example 1-18 UDL-18 2918 2916 100 350° C. × 60 sec Example 1-19UDL-19 2956 2955 100 350° C. × 60 sec Example 1-20 UDL-20 2934 2933 100350° C. × 60 sec Example 1-21 UDL-21 2949 2948 100 350° C. × 60 secExample 1-22 UDL-22 2975 2973 100 350° C. × 60 sec Example 1-23 UDL-232919 2919 100 350° C. × 60 sec Comparative Comparative 2928 2927 100350° C. × 60 sec Example 1-1 UDL-1 Comparative Comparative 2956 2955 100350° C. × 60 sec Example 1-2 UDL-2 Comparative Comparative 2928 2928 100250° C. × 60 sec Example 1-3 UDL-3 Comparative Comparative Poor film-350° C. × 60 sec Example 1-4 UDL-4 formation Comparative Comparative2928 2925 100 350° C. × 60 sec Example 1-5 UDL-5

As shown in Table 2, in either of the resist underlayer films using anyof the organic film compositions (UDL-1 to 23), it could be understoodthat they were all good film-forming property (mirror surface state),and, there were substantially no decrease in the film thickness by thesolvent treatment whereby films with solvent resistance could beobtained. On the other hand, in Comparative UDL-4 in which the liquidstate additive (B1) had been formulated with a significant amount,film-formation was poor (like a frosted glass), so that it was necessaryto reduce the loading amount thereof.

Etching Test in CF₄/CHF₃-Based Gas Examples 2-1 to 2-23, ComparativeExamples 2-1 to 2-4

The resist underlayer films were formed in the same manner as mentionedabove, and an etching test with a CF₄/CHF₃-based gas was carried outunder the following conditions.

Etching conditions Chamber pressure 40.0 Pa RF power 1,300 W CHF₃ gasflow rate 30 ml/min CF₄ gas flow rate 30 ml/min Ar gas flow rate 100ml/min Time 60 sec

By using an etching apparatus TE-8500 product of Tokyo Electron Limited,the remained films before and after etching were measured. The resultsare shown in Table 3.

TABLE 3 Film thickness Film thickness before etching: after etching: b/a× Composition a (Å) b (Å) 100 (%) Example 2-1 UDL-1 2987 1851 62 Example2-2 UDL-2 2857 1776 62.2 Example 2-3 UDL-3 2867 1788 62.4 Example 2-4UDL-4 2834 1842 65 Example 2-5 UDL-5 2872 1809 63 Example 2-6 UDL-6 28541866 65.4 Example 2-7 UDL-7 2776 1730 62.3 Example 2-8 UDL-8 2810 182164.8 Example 2-9 UDL-9 2892 1798 62.2 Example 2-10 UDL-10 2948 1859 63.1Example 2-11 UDL-11 2837 1756 61.9 Example 2-12 UDL-12 2898 1910 65.9Example 2-13 UDL-13 2930 1890 64.5 Example 2-14 UDL-14 2747 1802 65.6Example 2-15 UDL-15 2857 1768 61.9 Example 2-16 UDL-16 2874 1768 61.5Example 2-17 UDL-17 2857 1780 62.3 Example 2-18 UDL-18 2911 1808 62.1Example 2-19 UDL-19 2820 1856 65.8 Example 2-20 UDL-20 2859 1873 65.5Example 2-21 UDL-21 2798 1710 61.1 Example 2-22 UDL-22 2852 1771 62.1Example 2-23 UDL-23 2884 1883 65.3 Comparative Comparative 2781 178564.2 Example 2-1 UDL-1 Comparative Comparative 2956 1853 62.7 Example2-2 UDL-2 Comparative Comparative 2762 1815 65.7 Example 2-3 UDL-3Comparative Comparative 2928 1723 58.8 Example 2-4 UDL-5

As shown in Table 3, it could be confirmed that the resist underlayerfilm compositions (UDL-1 to 23) using the organic film compositions hadthe same or superior etching resistance to those of the comparativeunderlayer compositions (Comparative UDL-1 to 3, 5). Among the resistunderlayer film compositions, UDL-4 to 8 correspond to ComparativeUDL-1, UDL-9 to Comparative UDL-2, and UDL-10 to Comparative UDL-3,respectively.

On the other hand, as stated hereinbelow, whereas the liquid stateadditive (B1) is effective for improvement of filling property andplanarizing characteristics, in Comparative UDL-5, a film remaining rateby etching became small as compared with that of UDL-1 to which no (B1)had been formulated, so that it could be understood that it deterioratesetching resistance.

Evaluation of Filling Property Examples 3-1 to 3-23, ComparativeExamples 3-1 to 3-4

As shown in FIGS. 2G-2I, the resist underlayer film compositions wereeach coated on a SiO₂ wafer substrate having a dense hole pattern (holediameter: 0.16 μm, hole depth: 0.50 μm, distance between the centers ofthe adjacent two holes: 0.32 μm), and heated by using a hot plate at180° C. for 60 seconds, to form a resist underlayer film 8. Thesubstrate used is a basis substrate 7 (SiO₂ wafer substrate) having adense hole pattern as shown in FIG. 2G (downward view) and FIG. 2H(sectional view). Cross-sectional shapes of the obtained respectivewafer substrates were observed by using a scanning electron microscope(SEM), and whether inside of the hole was filled by the resistunderlayer film without voids or not was confirmed. The results areshown in Table 4. When a resist underlayer film composition inferior infilling property is used, voids occur at the inside of the hole in thisevaluation. When the resist underlayer film compositions having goodfilling property are employed, in this evaluation, the resist underlayerfilm is filled without any voids at the inside of the hole as shown inFIG. 2I.

TABLE 4 Presence or Composition absence of voids Example 3-1 UDL-1 NoneExample 3-2 UDL-2 None Example 3-3 UDL-3 None Example 3-4 UDL-4 NoneExample 3-5 UDL-5 None Example 3-6 UDL-6 None Example 3-7 UDL-7 NoneExample 3-8 UDL-8 None Example 3-9 UDL-9 None Example 3-10 UDL-10 NoneExample 3-11 UDL-11 None Example 3-12 UDL-12 None Example 3-13 UDL-13None Example 3-14 UDL-14 None Example 3-15 UDL-15 None Example 3-16UDL-16 None Example 3-17 UDL-17 None Example 3-18 UDL-18 None Example3-19 UDL-19 None Example 3-20 UDL-20 None Example 3-21 UDL-21 NoneExample 3-22 UDL-22 None Example 3-23 UDL-23 None ComparativeComparative Present Example 3-1 UDL-1 Comparative Comparative PresentExample 3-2 UDL-2 Comparative Comparative Present Example 3-3 UDL-3Comparative Comparative None Example 3-4 UDL-5

As shown in Table 4, it can be confirmed that the resist underlayer filmcompositions (UDL-1 to 23) can fill the hole pattern without any voids,and have excellent filling property as compared with those of thecomparative underlayer compositions (Comparative UDL-1 to 3). InComparative UDL-5, voids appeared in Comparative UDL-1 were eliminated,and it can be understood that the liquid state additive (B1) iseffective for the improvement of the filling property. However, asstated above, addition of (B1) is accompanied by deterioration ofetching resistance so that it is not preferred as an underlayercomposition.

Evaluation of Planarizing Characteristics Examples 4-1 to 4-23,Comparative Examples 4-1 to 4-4

The resist underlayer film compositions were each coated on a basissubstrate 9 (SiO₂ wafer substrate) having a giant isolated trenchpattern (FIG. 3J, trench width: 10 μm, trench depth: 0.50 μm), and afterbaking these compositions under the conditions shown in Table 5, adifference in film thicknesses at the trench portion and the non-trenchportion of the resist underlayer film 10 (delta 10 in FIG. 3K) wasobserved by using a scanning electron microscope (SEM). The results areshown in Table 5. In this evaluation, as the difference between the filmthicknesses is small, planarizing characteristics can be said to begood. Incidentally, in this evaluation, the trench pattern having adepth of 0.50 μm is planarized by using a resist underlayer filmcomposition having a usual film thickness of about 0.3 μm, so that thisis a specific severe evaluation condition to evaluate superiority orinferiority of the planarizing.

TABLE 5 Baking Difference in film Composition temperature thicknesses(nm) Example 4-1 UDL-1 180° C. × 60 sec + 140 350° C. × 60 sec Example4-2 UDL-2 180° C. × 60 sec + 140 350° C. × 60 sec Example 4-3 UDL-3 180°C. × 60 sec + 140 350° C. × 60 sec Example 4-4 UDL-4 180° C. × 60 sec +160 350° C. × 60 sec Example 4-5 UDL-5 180° C. × 60 sec + 160 350° C. ×60 sec Example 4-6 UDL-6 180° C. × 60 sec + 170 350° C. × 60 sec Example4-7 UDL-7 180° C. × 60 sec + 150 350° C. × 60 sec Example 4-8 UDL-8 180°C. × 60 sec + 160 350° C. × 60 sec Example 4-9 UDL-9 180° C. × 60 sec +160 350° C. × 60 sec Example 4-10 UDL-10 180° C. × 60 sec + 150 250° C.× 60 sec Example 4-11 UDL-11 180° C. × 60 sec + 170 350° C. × 60 secExample 4-12 UDL-12 180° C. × 60 sec + 150 350° C. × 60 sec Example 4-13UDL-13 180° C. × 60 sec + 150 350° C. × 60 sec Example 4-14 UDL-14 180°C. × 60 sec + 160 350° C. × 60 sec Example 4-15 UDL-15 180° C. × 60sec + 140 300° C. × 60 sec Example 4-16 UDL-16 180° C. × 60 sec + 160350° C. × 60 sec Example 4-17 UDL-17 180° C. × 60 sec + 150 350° C. × 60sec Example 4-18 UDL-18 180° C. × 60 sec + 140 350° C. × 60 sec Example4-19 UDL-19 180° C. × 60 sec + 150 350° C. × 60 sec Example 4-20 UDL-20180° C. × 60 sec + 150 350° C. × 60 sec Example 4-21 UDL-21 180° C. × 60sec + 130 300° C. × 60 sec Example 4-22 UDL-22 180° C. × 60 sec + 140350° C. × 60 sec Example 4-23 UDL-23 180° C. × 60 sec + 140 350° C. × 60sec Comparative Comparative 180° C. × 60 sec + 290 Example 4-1 UDL-1350° C. × 60 sec Comparative Comparative 180° C. × 60 sec + 320 Example4-2 UDL-2 350° C. × 60 sec Comparative Comparative 180° C. × 60 sec +280 Example 4-3 UDL-3 250° C. × 60 sec Comparative Comparative 180° C. ×60 sec + 230 Example 4-4 UDL-5 350° C. × 60 sec

As shown in Table 5, the resist underlayer film compositions (UDL-1 to23) were all small in the difference between film thicknesses of theresist underlayer film at the trench portion and the non-trench portion,as compared with those of the comparative underlayer compositions(Comparative UDL-1 to 3, 5), whereby it could be confirmed that theywere excellent in planarizing characteristics.

Pattern Formation Test Examples 5-1 to 5-23

The respective resist underlayer film compositions (UDL-1 to 23) wereeach coated on a SiO₂ wafer substrate having a trench pattern (trenchwidth: 10 μm, trench depth: 0.10 μm), and baked by the conditionsdescribed in Table 8 to prepare resist underlayer films. The resistmiddle layer film composition SOG1 was each coated thereon and baked at200° C. for 60 seconds to form a resist middle layer film having a filmthickness of 35 nm, and an SL resist for ArF of a resist upper layerfilm composition was coated thereon and baked at 105° C. for 60 secondsto form a photoresist film having a film thickness of 100 nm. The liquidimmersion protective film composition (TC-1) was coated on thephotoresist film, and baked at 90° C. for 60 seconds to form aprotective film having a film thickness of 50 nm.

As the resist middle layer film composition (SOG-1), 2% propylene glycolethyl ether solution of the following polymer was prepared.

In a solvent containing 0.1% by mass of FC-430 (product of Sumitomo 3MLimited) were dissolved a resin shown by RP1, an acid generator PAG1 anda base compound Amine 1 as resist upper layer film compositions (singlelayer resist for ArF) with a ratio shown in Table 6, and the mixture wasfiltered through a 0.1 μm filter made of a fluorine resin to prepare acomposition.

TABLE 6 Acid Base Polymer generator compound Solvent (parts by (parts by(part by (parts by No. mass) mass) mass) mass) Single layer RP1 PAG1Amine 1 PGMEA resist for ArF (100) (6.6) (0.8) (2,500)

The used RP1, PAG1 and Amine 1 are shown below.

As a liquid immersion protective film composition (TC-1), the polymerPP1 was dissolved in an organic solvent with a ratio shown in Table 7,and the solution was filtered by a 0.1 μm filter made of a fluorineresin to prepare the composition.

TABLE 7 Polymer Solvent No. (parts by mass) (parts by mass) TC-1 PP1Diisoamyl ether (2,700) (100) 2-methyl-1-butanol (270)

The used polymer PP1 is shown below.

Then, the composition was exposed by using ArF liquid immersion exposureapparatus (NSR-S610C product of Nikon Corporation, NA1.30, σ 0.98/0.65,35° dipole s polarizing illumination, 6% half-tone phase shift mask),baked at 100° C. for 60 seconds (PEB), and developed by 2.38% by massaqueous tetramethylammonium hydroxide (TMAH) solution for 30 seconds, toobtain 55 nm 1:1 positive-type line-and-space pattern.

Subsequently, the resist middle layer film was subjected to etchingprocessing by using the resist pattern as a mask due to dry etchingusing an etching apparatus Telius product of Tokyo Electron Limited, theresist underlayer film was subjected to etching by using the obtainedpattern-formed resist middle layer film as a mask, and the SiO₂ film wassubjected to etching processing by using the obtained pattern-formedresist underlayer film as a mask. The etching conditions are as shownbelow.

Transcription conditions of the resist pattern to the resist middlelayer film.

Chamber pressure 10.0 Pa RF power 1,500 W CF₄ gas flow rate 75 sccm O₂gas flow rate 15 sccm Time 15 sec

Transcription conditions of the pattern-formed resist middle layer filmto the resist underlayer film.

Chamber pressure 2.0 Pa RF power 500 W Ar gas flow rate 75 sccm O₂ gasflow rate 45 sccm Time 120 sec

Transcription conditions of the pattern-formed resist underlayer layerfilm to the SiO₂ film.

Chamber pressure 2.0 Pa RF power 2,200 W C₅F₁₂ gas flow rate 20 sccmC₂F₆ gas flow rate 10 sccm Ar gas flow rate 300 sccm O₂ 60 sccm Time 90sec

The pattern cross-section was observed by an electron microscope(S-4700) product of Hitachi, Ltd., and the results are shown in Table 8.

TABLE 8 Shape after substrate Baking transcription Compositiontemperature and etching Example UDL-1 180° C. × 60 sec + Perpendicular5-1 350° C. × 60 sec shape Example UDL-2 180° C. × 60 sec +Perpendicular 5-2 350° C. × 60 sec shape Example UDL-3 180° C. × 60sec + Perpendicular 5-3 350° C. × 60 sec shape Example UDL-4 180° C. ×60 sec + Perpendicular 5-4 350° C. × 60 sec shape Example UDL-5 180° C.× 60 sec + Perpendicular 5-5 350° C. × 60 sec shape Example UDL-6 180°C. × 60 sec + Perpendicular 5-6 350° C. × 60 sec shape Example UDL-7180° C. × 60 sec + Perpendicular 5-7 350° C. × 60 sec shape ExampleUDL-8 180° C. × 60 sec + Perpendicular 5-8 350° C. × 60 sec shapeExample UDL-9 180° C. × 60 sec + Perpendicular 5-9 350° C. × 60 secshape Example UDL-10 180° C. × 60 sec + Perpendicular 5-10 250° C. × 60sec shape Example UDL-11 180° C. × 60 sec + Perpendicular 5-11 350° C. ×60 sec shape Example UDL-12 180° C. × 60 sec + Perpendicular 5-12 350°C. × 60 sec shape Example UDL-13 180° C. × 60 sec + Perpendicular 5-13350° C. × 60 sec shape Example UDL-14 180° C. × 60 sec + Perpendicular5-14 350° C. × 60 sec shape Example UDL-15 180° C. × 60 sec +Perpendicular 5-15 300° C. × 60 sec shape Example UDL-16 180° C. × 60sec + Perpendicular 5-16 350° C. × 60 sec shape Example UDL-17 180° C. ×60 sec + Perpendicular 5-17 350° C. × 60 sec shape Example UDL-18 180°C. × 60 sec + Perpendicular 5-18 350° C. × 60 sec shape Example UDL-19180° C. × 60 sec + Perpendicular 5-19 350° C. × 60 sec shape ExampleUDL-20 180° C. × 60 sec + Perpendicular 5-20 350° C. × 60 sec shapeExample UDL-21 180° C. × 60 sec + Perpendicular 5-21 300° C. × 60 secshape Example UDL-22 180° C. × 60 sec + Perpendicular 5-22 350° C. × 60sec shape Example UDL-23 180° C. × 60 sec + Perpendicular 5-23 350° C. ×60 sec shape

As a result of this test, in either of the cases, the upper layer resistpattern was finally transferred to the substrate well, and it can beconfirmed that the resist underlayer film composition can be suitablyused for fine processing by the multilayer resist process, even on asubstrate having a step(s).

It must be stated here that the present invention is not restricted tothe embodiments shown by the embodiments. The embodiments are merelyexamples so that any embodiments composed of substantially the sametechnical concept as disclosed in the claims and expressing a similareffect are included in the technical scope.

What is claimed is:
 1. A compound for forming an organic film, whereinthe compound contains a polymer having a partial structure representedby the following formula (vii-2),

wherein R¹ represents a linear, branched or cyclic monovalenthydrocarbon group having 1 to 20 carbon atoms, and a methylene groupconstituting R¹ may be substituted by an oxygen atom; a+b is 1, 2 or 3;c and d are each independently 0, 1 or 2; x represents 0 or 1, when x=0,then a=c=0; L₇ represents a linear, branched or cyclic divalent organicgroup having 1 to 20 carbon atoms, L_(8′) represents the partialstructure represented by the following formula (i), 0≦o<1, 0<p≦1 ando+p=1,

wherein the ring structures Ar3 represent a substituted or unsubstitutedbenzene ring or naphthalene ring; R⁰ represents a hydrogen atom or alinear, branched or cyclic monovalent organic group having 1 to 30carbon atoms; and L₀ represents a divalent organic group selected fromthe following:


2. An organic film composition comprising the compound for forming anorganic film according to claim 1, the organic film composition furthercomprising at least one selected from (A) a compound represented by thefollowing formula (iii), (B) a compound having a partial structurerepresented by the following formula (iv), (C-1) a polymer compoundhaving a partial structure represented by the following formula (iv) asa part of the repeating unit, (C-2) a polymer compound having a partialstructure represented by the following formula (v), (C-3) a polymercompound having a partial structure represented by the following formula(vi), and (C-4) a polymer compound having a partial structurerepresented by the following formula (vii), wherein the formula (iii) isrepresented by

wherein R¹ represents a linear, branched or cyclic monovalenthydrocarbon group having 1 to 20 carbon atoms, and the methylene groupconstituting R¹ may be substituted by an oxygen atom; a+b and a′+b′ areeach independently 1, 2 or 3; c, d, c′ and d′ are each independently 0,1 or 2; x and y each independently represent 0 or 1, when x=0, thena=c=0, and when y=0, then a′=c′=0; and L represents a partial structurerepresented by the formula (ii), the formula (iv) is represented by

wherein R¹ represents a linear, branched or cyclic monovalenthydrocarbon group having 1 to 20 carbon atoms, and the methylene groupconstituting R¹ may be substituted by an oxygen atom; c, d, c′ and d′are each independently 0, 1 or 2; x and y each independently represent 0or 1, when x=0, then c=0, and when y=0, then c′=0; L represents apartial structure represented by the formula (ii); L₂ represents alinear, branched or cyclic divalent organic group having 2 to 30 carbonatoms; and the methylene group constituting L₂ may be substituted by anoxygen atom or a carbonyl group, and the hydrogen atom constituting thestructure may be substituted by a hydroxyl group, the formula (v) isrepresented by

wherein R¹ represents a linear, branched or cyclic monovalenthydrocarbon group having 1 to 20 carbon atoms, and a methylene groupconstituting R¹ may be substituted by an oxygen atom; a+b and a′+b′ areeach independently 1, 2 or 3; c, d, c′ and d′ are each independently 0,1 or 2; x and y each independently represent 0 or 1, when x=0, thena=c=0, and when y=0, then a′=c′=0; and L represents a partial structurerepresented by the formula (ii); L₃ represents a linear, branched orcyclic divalent organic group having 1 to 20 carbon atoms, L₄ representsL₃, the partial structure represented by the following formula (i), orthe partial structure represented by the formula (ii), 0≦i≦1, 0≦j≦1 andi+j=1,

wherein Ar3, R⁰ and L₀ have the same meanings as defined above, theformula (vi) is represented by

wherein Ar1 and Ar2 have the same meanings as defined above; R¹represents a linear, branched or cyclic monovalent hydrocarbon grouphaving 1 to 20 carbon atoms, and a methylene group constituting R¹ maybe substituted by an oxygen atom; a+b and a′+b′ are each independently1, 2 or 3; c, d, c′ and d′ are each independently 0, 1 or 2; x and yeach independently represent 0 or 1, when x=0, then a=c=0, and when y=0,then a′=c′=0; L₅ represents a linear, branched or cyclic divalentorganic group having 1 to 20 carbon atoms, L₆ represents the partialstructure represented by the formula (ii), 0≦m<1, 0<n≦1 and m+n=1, andthe formula (vii) is represented by

wherein R¹ represents a linear, branched or cyclic monovalenthydrocarbon group having 1 to 20 carbon atoms, and a methylene groupconstituting R¹ may be substituted by an oxygen atom; a+b is 1, 2 or 3;c and d are each independently 0, 1 or 2; x represents 0 or 1, when x=0,then a=c=0; L₇ represents a linear, branched or cyclic divalent organicgroup having 1 to 20 carbon atoms, L₈ represents the partial structurerepresented by the formula (ii), 0≦o<1, 0<p≦1 and o+p=1.
 3. The organicfilm composition according to claim 2, wherein the composition contains(D) a resin containing an aromatic ring which is different from thepolymers (C-1) to (C-4).
 4. The organic film composition according toclaim 3, wherein (D) the resin containing an aromatic ring contains anaphthalene ring.
 5. The organic film composition according to claim 3,wherein (D) the resin containing an aromatic ring contains a resin (D-1)obtained by polycondensating one or more kinds of compounds representedby the following formulae (3a) and (3b), and a compound represented bythe following formula (4),

wherein each R² independently represent a hydrogen atom or a saturatedor unsaturated hydrocarbon group having 1 to 20 carbon atoms; each R³independently represent a benzene ring or a naphthalene ring; m1+m2,m3+m4 and m5+m6 are each 1 or 2; n1, n2 and n3 are each 0 or 1,A-CHO  (4) wherein A represents a hydrogen atom, a hydrocarbon grouphaving 1 to 10 carbon atoms, or a substituted or unsubstituted aromatichydrocarbon group having 6 to 20 carbon atoms.
 6. The organic filmcomposition according to claim 3, wherein (D) the resin containing anaromatic ring contains a resin (D-2) having one or more of a repeatingunit(s) represented by the following formula (5),

wherein each R⁴ independently represent a hydrogen atom or a saturatedor unsaturated hydrocarbon group having 1 to 20 carbon atoms; R⁵represents a hydrogen atom or may form a ring by bonding to one of R⁴;when R⁴ and R⁵ are bonded to form a ring, —R⁴—R⁵— represents a singlebond or an alkylene group having 1 to 3 carbon atoms; m7+m8 is 0, 1 or2; and n4 is 0 or
 1. 7. The organic film composition according to claim2, wherein the composition further comprises at least one of (E) acompound containing a phenolic hydroxyl group, (F) an acid generator,(G) a cross-linking agent, (H) a surfactant and (I) an organic solvent.8. The organic film composition according to claim 2, wherein it is usedas a resist underlayer film composition or a planarizing composition formanufacturing a semiconductor apparatus.
 9. A process for forming anorganic film which acts as a resist underlayer film or a planarizingfilm for manufacturing a semiconductor apparatus of a multilayer resistfilm used in lithography, which comprises coating the organic filmcomposition according to claim 2 on a substrate to be processed, andsubjecting the composition to heat treatment at a temperature of 100° C.or higher and 600° C. or lower for 10 seconds to 600 seconds to form acured film.
 10. A process for forming an organic film which acts as aresist underlayer film or a planarizing film for manufacturing asemiconductor apparatus of a multilayer resist film used in lithography,which comprises coating the organic film composition according to claim8 on a substrate to be processed, and subjecting the composition to heattreatment at a temperature of 100° C. or higher and 600° C. or lower for10 seconds to 600 seconds to form a cured film.
 11. A process forforming an organic film which acts as a resist underlayer film or aplanarizing film for manufacturing a semiconductor apparatus of amultilayer resist film used in lithography, which comprises coating theorganic film composition according to claim 2 on a substrate to beprocessed, and baking the composition in an atmosphere with an oxygenconcentration of 0.1% or more and 21% or less to form a cured film. 12.A process for forming an organic film which acts as a resist underlayerfilm or a planarizing film for manufacturing a semiconductor apparatusof a multilayer resist film used in lithography, which comprises coatingthe organic film composition according to claim 8 on a substrate to beprocessed, and baking the composition in an atmosphere with an oxygenconcentration of 0.1% or more and 21% or less to form a cured film. 13.The method for forming an organic film according to claim 9, wherein thesubstrate to be processed is a substrate to be processed having astructural composition or step(s) each with a height of 30 nm or more.14. The method for forming an organic film according to claim 10,wherein the substrate to be processed is a substrate to be processedhaving a structural composition or step(s) each with a height of 30 nmor more.
 15. The method for forming an organic film according to claim11, wherein the substrate to be processed is a substrate to be processedhaving a structural composition or step(s) each with a height of 30 nmor more.
 16. The method for forming an organic film according to claim12, wherein the substrate to be processed is a substrate to be processedhaving a structural composition or step(s) each with a height of 30 nmor more.
 17. A patterning process which is a process for forming apattern on a substrate to be processed, which comprises the steps of, atleast, forming a resist underlayer film by using the organic filmcomposition according to claim 2 on the substrate to be processed;forming a resist middle layer film composition on the resist underlayerfilm using a resist middle layer film composition containing a siliconatom; forming a resist upper layer film on the resist middle layer filmby using a resist upper layer film composition comprising a photoresistcomposition, to form a multilayer resist film; conducting exposure of apattern circuit region of the resist upper layer film and thendeveloping it with a developer to form a resist pattern on the resistupper layer film; etching the resist middle layer film by using thepattern-formed resist upper layer film as an etching mask; etching theresist underlayer film by using the pattern-formed resist middle layerfilm as an etching mask; and further etching the substrate to beprocessed by using the obtained pattern-formed resist underlayer film asan etching mask, to form a pattern on the substrate to be processed. 18.The patterning process according to claim 17, wherein etching of theresist underlayer film by using the resist middle layer film as anetching mask is performed by using an etching gas mainly comprising anoxygen gas or a hydrogen gas.
 19. A patterning process which is aprocess for forming a pattern on a substrate to be processed, whichcomprises the steps of, at least, forming a resist underlayer film byusing the organic film composition according to claim 2 on the substrateto be processed; forming an inorganic hard mask middle layer filmselected from any one of a silicon oxide film, a silicon nitride filmand a silicon oxynitride film on the resist underlayer film; forming aresist upper layer film on the inorganic hard mask middle layer film byusing a resist upper layer film composition comprising a photoresistcomposition, to prepare a multilayer resist film; conducting exposure ofa pattern circuit region of the resist upper layer film and thendeveloping it with a developer to form a resist pattern on the resistupper layer film; etching the inorganic hard mask middle layer film byusing the obtained resist pattern as an etching mask; etching the resistunderlayer film by using the obtained pattern-formed inorganic hard maskmiddle layer film as an etching mask; and further etching the substrateto be processed by using the obtained pattern-formed resist underlayerfilm as an etching mask, to form a pattern on the substrate to beprocessed.
 20. A patterning process which is a process for forming apattern on a substrate to be processed, which comprises the steps of, atleast, forming a resist underlayer film by using the organic filmcomposition according to claim 2 on the substrate to be processed;forming an inorganic hard mask middle layer film selected from any oneof a silicon oxide film, a silicon nitride film and a silicon oxynitridefilm on the resist underlayer film; forming an organic antireflectionfilm on the inorganic hard mask middle layer film; forming a resistupper layer film on the organic antireflection film by using a resistupper layer film composition comprising a photoresist composition, toprepare a multilayer resist film; conducting exposure of a patterncircuit region of the resist upper layer film and then developing itwith a developer to form a resist pattern on the resist upper layerfilm; etching the organic antireflection film and the inorganic hardmask middle layer film by using the obtained resist pattern as anetching mask; etching the resist underlayer film by using the obtainedpattern-formed inorganic hard mask middle layer film as an etching mask;and further etching the substrate to be processed by using the obtainedpattern-formed resist underlayer film as an etching mask, to form apattern on the substrate to be processed.
 21. The patterning processaccording to claim 19, wherein the inorganic hard mask middle layer filmis formed by a CVD method or an ALD method.
 22. The patterning processaccording to claim 20, wherein the inorganic hard mask middle layer filmis formed by a CVD method or an ALD method.
 23. The patterning processaccording to claim 19, wherein the substrate to be processed is asubstrate to be processed having a structural composition or step(s)each with a height of 30 nm or more.
 24. The patterning processaccording to claim 20, wherein the substrate to be processed is asubstrate to be processed having a structural composition or step(s)each with a height of 30 nm or more.